CN109414854B - Method for producing resin composite molded article - Google Patents
Method for producing resin composite molded article Download PDFInfo
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- CN109414854B CN109414854B CN201780042053.1A CN201780042053A CN109414854B CN 109414854 B CN109414854 B CN 109414854B CN 201780042053 A CN201780042053 A CN 201780042053A CN 109414854 B CN109414854 B CN 109414854B
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- 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
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Abstract
The invention provides a resin compositeThe strength of the composite molded body can be further improved when the composite molded body is joined to another molded body, without being restricted by the presence or absence of the inorganic filler in the resin molded body and the color of the resin molded body. The production method of the present invention includes an injection step of injecting a thermoplastic or thermosetting 2 nd resin composition into a concave-convex surface (11) of a1 st resin molded body (10) having concave-convex surfaces, which is formed of a cured product of the 1 st resin composition (fig. 1 (B)). The difference between the temperature of the 2 nd resin composition in the injection step and the Vicat softening point of the 1 st resin molded body (10) is 15 ℃ to 300 ℃. In the resin composite molded article (1), when L (mm) represents the height of the convex portion (13) of the 1 st resin molded article (10), d (mm) represents the width of the convex portion (13) in the direction parallel to the direction in which the 2 nd resin composition is injected, and b (mm) represents the width of the convex portion (13) in the direction perpendicular to the direction in which the 2 nd resin composition is injected, 6L/bd2The value of (A) is 5 to 600 inclusive.
Description
Technical Field
The present invention relates to a method for producing a resin composite molded article.
Background
In recent years, in the fields represented by automobiles, electric products, industrial equipment, and the like, in response to a demand for reduction in carbon dioxide emission, reduction in manufacturing cost, and the like, a metal molded body has been replaced with a resin molded body. Accordingly, there is a demand for providing a technique for firmly integrating one resin molded body with another resin molded body.
Patent document 1 discloses a method of manufacturing a composite molded article by integrating one resin molded article with another molded article. In this method, a grooved resin molded body is obtained by removing a part of the resin from a resin molded article containing a fibrous inorganic filler to form grooves in which the inorganic filler is exposed from the side surface, and then the grooved surface of the grooved resin molded body is integrated with another molded body as a contact surface. In order to obtain a grooved resin molded body, a part of the resin is removed by laser irradiation. According to this method, the inorganic filler exposed in the groove exerts an anchoring effect of suppressing the destruction of the grooved resin molded body and another molded body, and as a result, the strength of the composite molded body can be remarkably improved.
Further, patent document 2 discloses an insert molding method in which a resin molded part is inserted into a mold, and a resin is injection molded around the resin molded part to integrate the resin with the resin molded part. In this method, either one of a specific resin a (polyacetal resin, polyamide resin, or polypropylene resin) and a specific resin B (styrene resin such as ABS resin or polycarbonate resin) is used as a molding material for a resin molded part to be inserted into a mold, and the other of the specific resins A, B is used as a resin for injection molding. Further, projections such as ribs are formed at appropriate positions of the resin molded part inserted into the mold, and the projections such as ribs are deformed by the resin injected at the time of insert molding or insert molding (japanese patent No. アウトサート) and remain in the resin injected. According to this method, since the projection such as the rib formed in advance on the resin molded part inserted into the mold is deformed by injection molding and remains in the resin to be injection molded, even when the resins which are not welded to each other are peeled off at the contact surface, the deformed projection such as the rib connects the molded portions to each other like a wedge, and the molded portion of the resin on one side can be suppressed from falling off.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 5632567
Patent document 2: japanese laid-open patent publication No. 7-137089
Disclosure of Invention
Problems to be solved by the invention
However, in the method described in patent document 1, since the inorganic filler exposed in the groove is used as an anchor, at least one of the resin molded bodies needs to contain the inorganic filler. Therefore, it is desired to provide a technique for firmly joining two resin molded bodies constituting a resin composite molded body even when both the resin molded bodies do not contain an inorganic filler.
In the method described in patent document 1, since a part of the resin in the resin molded article containing the fibrous inorganic filler is removed by laser irradiation, it is necessary to make the color of the resin molded article a color having high laser absorptivity. Therefore, in the method described in patent document 1, the color of the resin molded article containing the fibrous inorganic filler is restricted.
In addition, in the method described in patent document 2, there is room for improvement in the bonding strength at the bonding interface.
The present invention has been made to solve the above-described problems, and an object thereof is to provide a resin composite molded article which is not restricted by the presence or absence of an inorganic filler in the resin molded article and the color of the resin molded article and can further improve the strength when the resin composite molded article is joined to another molded article.
Means for solving the problems
The present inventors have made extensive studies to solve the above problems. As a result, the present inventors have found that the above problems can be solved by setting the injection temperature at the time of injecting the 2 nd resin composition onto the surface of the 1 st resin molded body within a predetermined range and setting the shape of the surface of the 1 st resin molded body to a predetermined shape, and have completed the present invention. Specifically, the present invention provides the following technical means.
(1) The method for producing a resin composite molded article of the present invention includes an injection step of injecting a thermoplastic or thermosetting 2 nd resin composition into a surface of a1 st resin molded article, which is composed of a cured product of the 1 st resin composition that is thermoplastic and does not contain a coloring agent for absorbing laser light and has irregularities formed on the surface thereof by injection molding, and the resin composite molded article passes through the injection stepIn the method for producing a resin composite molded article in which the 1 st resin molded article and the 2 nd resin molded article composed of a cured product of the 2 nd resin composition are joined, a value obtained by subtracting a vicat softening point of the 1 st resin molded article from a temperature of the 2 nd resin composition in the injection step is 15 ℃ to 300 ℃, and when a height of a convex portion of the unevenness of the 1 st resin molded article is represented by L, a width of the convex portion in a direction parallel to a direction in which the 2 nd resin composition is injected is represented by d, and a width of the convex portion in a direction perpendicular to the direction in which the 2 nd resin composition is injected is represented by b, 6L/bd is obtained in the resin composite molded article2The value of (A) is 5 to 600 inclusive, wherein the units of L, d and b are mm.
(2) In the present invention, according to the method for producing a resin composite molded article according to (1), the resin constituting the 1 st resin composition is the same as the resin constituting the 2 nd resin composition.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide a resin composite molded article which is not restricted by the presence or absence of an inorganic filler in the resin molded article and the color of the resin molded article and which can further improve the strength when joined to another molded article.
Drawings
Fig. 1 is a schematic diagram showing an example of a method for producing a resin composite molded article 1 according to the present embodiment.
Fig. 2 is a schematic view showing a state of the uneven surface 11 of the 1 st resin molded article 10 of the resin composite molded article 1.
Fig. 3 is a diagram showing a modification of the uneven surface 11.
Fig. 4 is a schematic diagram illustrating the tendency of the convex portions 13 of the uneven surface 11 to fall down when the 2 nd resin composition is injected at an injection pressure p (n) against the uneven surface 11 of the 1 st resin molded article 10.
Fig. 5 is a graph showing the results of measuring the breaking load in test example 2.
Fig. 6 is a graph showing the results of measuring the breaking load in test example 3.
Fig. 7 is a view showing a cross section when the resin composite molded article 1 of test example 1-3 is cut downward from above so that the boundary between the 1 st resin molded article 10 and the 2 nd resin molded article 20 can be observed.
Detailed Description
The embodiments of the present invention will be described in detail below, but the present invention is not limited to the embodiments below, and can be implemented with appropriate modifications within the scope of the object of the present invention. Note that, although description of parts overlapping description may be omitted as appropriate, the gist of the present invention is not limited thereto.
< method for producing resin composite molded article >
Fig. 1 is a schematic diagram showing an example of the production method according to the present embodiment.
In the manufacturing method of the present embodiment, first, as shown in fig. 1 a, the 1 st resin composition (1 st resin) is molded 1 time using an injection molding die having an uneven surface formed thereon to obtain the 1 st resin molded article 10 having the uneven surface 11 having an uneven surface on the surface (1 st molding step).
Next, as shown in fig. 1B, the 1 st resin molded article 10 is placed in a mold (not shown), and an uncured 2 nd resin composition is injected into the mold with the uneven surface 11 as a contact surface (injection step). Then, the 2 nd resin composition is cured, and the 1 st resin molded article 10 is integrated with the 2 nd resin molded article 20 made of a cured product of the 2 nd resin composition, to obtain the resin composite molded article 1.
[1 Forming Process ]
[1 st resin composition ]
The resin constituting the 1 st resin composition is not particularly limited as long as it is a thermoplastic resin. Examples of the preferable resin include Polyacetal (POM), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), and Liquid Crystal Polymer (LCP).
[ injection Molding die ]
The injection molding die has a structure in which a concave-convex portion is formed on a molding surface thereof and a shape can be transferred to an object to be injection molded, but this portion is not illustrated.
[1 st resin molded article 10]
Fig. 2 (a) is a schematic view showing a state of the uneven surface 11 of the first resin molded body 10, and fig. 2 (B) is a partially enlarged view of the uneven surface 11. The uneven surface 11 includes a concave portion 12 (corresponding to a "groove") and a convex portion 13 (corresponding to a "mountain").
By alternately forming the plurality of concave portions 12 and the plurality of convex portions 13, the 1 st resin molded body 10 and the 2 nd resin molded body 20 can be more firmly joined.
In fig. 2, the configuration in which the shape of the uneven surface 11 is a mesh shape (the shape in which the convex portions 13 are formed in a mesh shape) is described, but the shape of the uneven surface 11 is not particularly limited. For example, as shown in fig. 3 a, the shape of the uneven surface 11 may be a stripe shape (a shape in which the concave portions 12 and the convex portions 13 are alternately formed in a stripe shape), or as shown in fig. 3B, the shape of the uneven surface 11 may be a contour shape (a shape in which the concave portions 12 and the convex portions 13 are alternately formed in a contour line). As shown in fig. 3C, the uneven surface 11 may have a cross-hatched shape (a shape in which the convex portions 13 are arranged obliquely with respect to the side of the uneven surface 11). The shape of the uneven surface 11 is preferably a mesh shape from the point where the 1 st resin molded body 10 and the 2 nd resin molded body 20 can be more firmly joined.
The shape of the convex portion 13 is not limited to a quadrangle, and may be a circle or an ellipse, but these parts are not illustrated.
When the height of the convex portion 13 of the 1 st resin molded body 10 is L (mm), the width of the convex portion 13 in the 1 st direction is d (mm), and the width of the convex portion 13 in the 2 nd direction is b (mm), 6L/bd2Has a value of 600 or less. Here, the 1 st direction means a direction parallel to the direction in which the 2 nd resin composition is injected, and the 2 nd direction means a direction perpendicular to the direction in which the 2 nd resin composition is injected.
Fig. 4 is a schematic diagram for explaining the resistance to toppling of the convex portions 13 of the uneven surface 11 when the 2 nd resin composition is injected at the injection pressure p (n) against the uneven surface 11 of the 1 st resin molded article 10. The convex part 13 can be hardly inclined by the bending stress sigmab(MPa)Is expressed by the bending stress σbAt 6LP/bd2And (4) showing. In the present embodiment, wherein 6L/bd2The degree of difficulty in falling of the convex portion 13 was evaluated based on the magnitude of the coefficient a.
Coefficient a (6L/bd)2) The upper limit of (d) may be 600 or less, but is preferably 400 or less, more preferably 200 or less, and still more preferably 100 or less. If the coefficient a is too large, when the 2 nd resin composition is injected into the uneven surface 11 of the 1 st resin molded article 10, the convex portions 13 may fall over, and the uneven surface 11 may not sufficiently function as an anchor for suppressing the breakage of the 1 st resin molded article 10 and the 2 nd resin molded article 20.
In addition, the coefficient a of the convex portion 13 of the molded article being large means that the convex portion 13 has a slender shape, and a slender concave structure corresponding to the convex portion 13 is provided on the mold side for molding the convex portion 13, so that when the coefficient a is extremely large, difficulty is high from the viewpoint of mold manufacturing.
Coefficient a (6L/bd)2) The lower limit of (b) is not less than 5, but preferably not less than 10, more preferably not less than 20. If the coefficient a is too small, the uneven surface 11 may not sufficiently exhibit the anchoring function of suppressing the breakage of the 1 st resin molded article 10 and the 2 nd resin molded article 20.
The interval (pitch) P between adjacent convex portions 13 is not particularly limited, and P is preferably 1.5 to 4 times the width (groove width) W of the concave portion 12, that is, P is preferably 0.3 to 0.8mm when the groove width is 0.2mm, more preferably 2 to 3 times the groove width, that is, P is more preferably 0.4 to 0.6mm when the groove width is 0.2mm, in order to firmly join the 1 st resin molded body 10 and the 2 nd resin molded body 20. If the interval (pitch) P between the adjacent convex portions 13 is too small, the widths (b, d) of the convex portions 13 and the groove width W are both small, and therefore, the structural strength of the convex portions 13 of the 1 st resin molded article 10 and the structural strength of the portion of the 2 nd resin molded article 20 that enters the concave portion 12 of the 1 st resin molded article 10 are reduced, and therefore, the resin composite molded article 1 may be broken by a low external force.
Further, even if the interval (pitch) P between the adjacent convex portions 13 is large, if the groove width W is excessively small, the external force may be applied to the resin composite molded article 1 to cause the 2 nd resin molded article 20 to be broken by the low external force, and similarly, even if the interval (pitch) P between the adjacent convex portions 13 is large, if the widths (b, d) of the convex portions 13 are excessively small, the external force may be applied to the resin composite molded article 1 to cause the 1 st resin molded article 10 to be broken by the low external force.
[ injection procedure ]
The injection step is a step of placing the 1 st resin molded article 10 in a mold (not shown), and injecting the uncured 2 nd resin composition into the mold with the uneven surface 11 as a contact surface.
[2 nd resin composition ]
The resin constituting the 2 nd resin composition is a thermoplastic or thermosetting resin. In addition, when the melting point of the 2 nd resin composition is equal to or higher than the melting point of the 1 st resin composition, the temperature at the time of injecting the 2 nd resin composition tends to be higher than the heat distortion temperature of the 1 st resin composition in a normal case, and therefore, the effect of the later-described locking (japanese: かしめ) is easily obtained, but even if the melting point of the 2 nd resin composition is equal to or lower than the melting point of the 1 st resin composition, the 2 nd resin composition can be applied to the present invention as long as the 2 nd resin composition can be injected at a temperature higher than the heat distortion temperature of the 1 st resin composition.
When the melting point of the 2 nd resin composition is lower than the melting point of the 1 st resin composition, the shape coefficient a is preferably increased because the uneven surface 11 of the 1 st resin molded product 10 tends to be less likely to be thermally deformed when the uncured 2 nd resin composition is injected onto the uneven surface 11 of the 1 st resin molded product 10. The range of the shape coefficient a is preferably 100 or more, and more preferably 200 or more and 500 or less.
The resin constituting the 1 st resin composition and the resin constituting the 2 nd resin composition may be the same or different. Among them, the resin composite molded body 1 having high strength can be obtained as compared with the method described in patent document 1 (a resin molded body containing a fibrous inorganic filler is subjected to a process in which a part of the resin is removed from a resin molded article containing the fibrous inorganic filler to form a groove in which the inorganic filler is exposed from a side surface, and then the surface having the groove of the resin molded body is integrated with another molded body as a contact surface), and therefore, it is preferable that the resin constituting the resin composition 1 is the same as the resin constituting the resin composition 2.
[ injection of the resin composition ] of the formula
When the 2 nd resin composition is injected, the uncured 2 nd resin composition is disposed on the uneven surface of the 1 st resin molded body 10 at a temperature equal to or higher than the heat distortion temperature (vicat softening point) of the 1 st resin molded body 10. Thus, by thermally deforming a part of the uneven surface 11 of the 1 st resin molded body 10, the contact surface of the 2 nd resin molded body 20 with the 1 st resin molded body 10 can be locked to the surface of the 1 st resin molded body 10 by the unevenness.
The difference (Δ T) between the vicat softening point of the second resin composition in the injection step 2 and the vicat softening point of the first resin molded article 1 is 15 ℃ to 300 ℃, more preferably 30 ℃ to 110 ℃, still more preferably 40 ℃ to 90 ℃, still more preferably 45 ℃ to 80 ℃, and particularly preferably 50 ℃ to 70 ℃.
If the Δ T is too small, the uneven surface 11 of the 1 st resin molded body 10 cannot be sufficiently thermally deformed, and as a result, the 1 st resin molded body 10 and the 2 nd resin molded body 20 may not be appropriately joined, which is not preferable.
On the other hand, if Δ T is too large, the uneven surface 11 of the 1 st resin molded product 10 may melt, and the convex portions 13 of the uneven surface 11 may disappear, which is not preferable.
The injection pressure may be an injection pressure and a holding pressure after filling, which are sufficient to allow the 2 nd resin composition to enter the concave portion (groove) 12 of the 1 st resin molded article 10 and allow the uneven surface 11 of the 1 st resin molded article 10 to exhibit an anchoring effect.
The injection speed is an injection speed at which the uncured 2 nd resin composition enters the concave portion 12 at the time of injection press-fitting, and a stress is applied to a part of the convex portion 13 to deform and lock the convex portion 13.
[ curing Process ]
The curing step is a step of curing the uncured 2 nd resin composition supplied in the injection step to integrate the 1 st resin molded body 10 and the 2 nd resin molded body 20 made of a cured product of the 2 nd resin composition, thereby obtaining the resin composite molded body 1. After the 1-time molding step, the injection step, and the curing step, the resin composite molded article 1 molded multiple times is obtained.
[ evaluation of resin composite molded article 1]
As described above, regarding the 1 st resin molded article 10, the coefficient a (6L/bd)2) The value of (A) is 5 to 600 inclusive. In examining whether or not the coefficient a falls within the technical range of the present invention, the coefficient a was evaluated from the resin composite molded article 1.
The method of evaluating the coefficient a from the resin composite molded article 1 may include the following methods: (1) evaluation by X-ray CT; (2) dissolving the 2 nd resin molded body 20 using a solvent which does not dissolve the 1 st resin molded body 10 but dissolves the 2 nd resin molded body 20, and evaluating the coefficient a for the remaining 1 st resin molded body 10; (3) the resin composite molded article 1 is cut so that the boundary between the 1 st resin molded article 10 and the 2 nd resin molded article 20 can be observed, and the boundary between the 1 st resin molded article 10 and the 2 nd resin molded article 20 is observed from the cut cross section. In the present embodiment, the coefficient a is evaluated by the method (3) described above, that is, the resin composite molded body 1 is cut so that the boundary between the 1 st resin molded body 10 and the 2 nd resin molded body 20 can be observed, and the boundary between the 1 st resin molded body 10 and the 2 nd resin molded body 20 is observed from the cut cross section, in view of the fact that the coefficient a can be evaluated simply and at low cost.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
< test example 1>1 time of the conditions of the molding step (shape of uneven surface 11)
[1 time formation ]
Polyphenylene sulfide resin (product name: DURAFIDE 0220A9, Vicat softening point: 250 ℃ C., manufactured by Corp. plastics Co., Ltd.) was injection-molded under the following conditions to obtain the plate-like first resin molded article 10 having a longitudinal length of 13mm, a lateral length of 65mm and a thickness of 6.5 mm.
Irregularities are formed on one side surface (6.5 mm in the vertical direction and 13mm in the horizontal direction) formed by the thickness direction and the vertical direction of the 1 st resin molded article 10. The shape of the convex portion 13 of the uneven surface 11 formed by the unevenness is shown in table 1. The width of each recess was 0.2 mm.
(conditions of 1-time Molding)
Preliminary drying: 140 ℃ for 3 hours
Barrel temperature: 320 deg.C
Temperature of the die: 150 ℃ C
Injection speed: 20mm/sec
Pressure maintaining: 50MPa
[ 2-time formation ]
The same resin as used in the molding of 1 st time was injection-molded under the same conditions as in the molding of 1 st time using the uneven surface 11 of the resin molded article 10 of 1 st time as a contact surface and a mold for injection molding having a cavity with a length of 13m, a width of 130mm and a thickness of 6.5mm was fitted therein to obtain a resin composite molded article 1.
[ evaluation ]
The joint strengths of the resin composite molded articles 1 of test examples 1-1 to 1-5 were measured. The measurement of the joint strength was performed by tensile peeling of the resin composite molded article 1 and measurement of the breaking load. The measurement apparatus used was a universal tensile machine UTA-50kN (manufactured by ORIENTEC corporation), and the crosshead speed was set to 10 mm/min. The results are shown in table 1.
[ Table 1]
As confirmed from test example 1, if the coefficient a (6L/bd)2) When the value of (3) is in the range of 5 to 600, the 1 st resin molded article 10 and the 2 nd resin molded article 20 can be intentionally prevented from being broken when the resin composite molded article 1 is obtained by integrating the uneven surface 11 of the 1 st resin molded article 10 as a contact surface with the 2 nd resin molded article 20.
< test example 2> comparison between conditions of 2 molding steps (injection temperature of 2 nd resin composition) and resin materials
[ Table 2]
In table 2, the materials of the 1 st resin composition and the 2 nd resin composition are as follows.
POM: polyacetal resin (product name: DURACON M90-44, Vicat softening point: 148 ℃ C., product of Gei plastics Co., Ltd.)
POM containing glass fibers: polyacetal resin containing glass fiber (product name: DURACONGH-25, Vicat softening point: 154 ℃, manufactured by Georgi plastics Co., Ltd.)
PBT: polybutylene terephthalate resin (product name: DURANEX2200, Vicat softening point: 190 ℃, manufactured by Baoli Plastic Co., Ltd.)
PBT containing glass fiber: glass fiber-containing polybutylene terephthalate resin (product name: DURANEX3300, Vicat softening point: 214 ℃ C., product of Baoli plastics Co., Ltd.)
PPS: polyphenylene sulfide resin (product name: DURAFIDE PPS 0220A9, Vicat softening point: 250 ℃, manufactured by Baoli plastics Co., Ltd.)
PPS containing glass fibers: polyphenylene sulfide resin containing glass fiber (product name: DURAFIDE PPS 1140A1, Vicat softening point: 266 ℃, manufactured by Georgi plastics Co., Ltd.)
PEEK containing glass fibers: polyether ether ketone resin containing glass fiber (product name: VESTAKEEP 2000GF30, manufactured by DAICEL EVONIK Co., Ltd.)
[ invention according to the present embodiment ]
First, a resin composite molded article 1 was obtained by the method described in the present embodiment.
[1 time formation ]
The resin composition 1 shown in Table 2 was injection-molded under the following conditions to obtain the same shape (coefficient a (6L/bd) as in test example 1-22) 38) of the 1 st resin molded article 10.
(conditions for injection Molding of POM and POM containing glass fiber)
Preliminary drying: 80 ℃ for 3 hours
Barrel temperature: 200 deg.C
Temperature of the die: 80 deg.C
Injection speed: 16mm/sec
Pressure maintaining: 50MPa
(conditions for injection Molding of PBT or glass fiber-containing PBT)
Preliminary drying: 140 ℃ for 3 hours
Barrel temperature: 260 deg.C
Temperature of the die: 60 deg.C
Injection speed: 20mm/sec
Pressure maintaining: 50MPa
(conditions for injection Molding of PPS and glass fiber-containing PPS)
Preliminary drying: 140 ℃ for 3 hours
Barrel temperature: 320 deg.C
Temperature of the die: 150 ℃ C
Injection speed: 20mm/sec
Pressure maintaining: 50MPa
[2 formation ]
The resin composite molded article 1 was obtained by using the uneven surface 11 of the 1 st resin molded article 10 as a contact surface, inserting the same mold for injection molding as in test example 1, and injection molding the 2 nd resin composition described in table 2. The difference between the temperature of the 2 nd resin composition (cylinder temperature) and the Vicat softening point of the 1 st resin molded article 10 was set to a plurality of values within the range of-66 ℃ to 252 ℃ as shown in Table 2. The conditions for injection molding differ depending on the type of resin constituting the 2 nd resin composition, as in the case of the 1 st molding.
The conditions for injection molding of PEEK containing glass fibers are as follows.
(conditions for injection Molding of PEEK containing glass fiber)
Preliminary drying: 140 ℃ for 3 hours
Barrel temperature: 400 deg.C
Temperature of the die: 180 deg.C
Injection speed: 20mm/sec
Pressure maintaining: 80MPa
[ evaluation ]
The joint strength was measured for each resin composite molded article 1 of test example 2 in the same manner as in test example 1. The results are shown in table 2 and fig. 5.
From the results of test example 2 shown in fig. 5, it can be said that when the difference (Δ T) between the temperature of the 2 nd resin composition at the time of injecting the 2 nd resin composition and the vicat softening point of the 1 st resin molded article 10 is 15 ℃ to 300 ℃, when the resin composite molded article 1 is obtained by integrating the 2 nd resin molded article 20 with the uneven surface 11 of the 1 st resin molded article 10 as a contact surface, a bonding strength of 10MPa or more can be obtained, and breakage of the 1 st resin molded article 10 and the 2 nd resin molded article 20 can be intentionally prevented.
From the results of test example 2, when the Δ T is 30 ℃ to 110 ℃, a bonding strength of 20MPa or more can be obtained. When the Δ T is 40 ℃ to 90 ℃, a bonding strength of 30MPa or more can be obtained. When the Δ T is 45 ℃ to 80 ℃, a bonding strength of 40MPa or more can be obtained. When the Δ T is 50 ℃ or more and 70 ℃ or less, a bonding strength of 50MPa or more can be obtained.
If Δ T is less than 15 ℃, sufficient bonding strength cannot be obtained even if the resin composite molded article 1 is obtained. This is presumably because the uneven surface 11 of the 1 st resin molded article 10 cannot be sufficiently thermally deformed by the injection of the 2 nd resin composition, and as a result, the 1 st resin molded article 10 and the 2 nd resin molded article 20 cannot be appropriately joined.
On the other hand, if Δ T is greater than 300 ℃, it is difficult to obtain sufficient bonding strength. This is presumably because the uneven surface 11 of the 1 st resin molded article 10 melts and the convex portions 13 of the uneven surface 11 tend to disappear.
(test examples 2-1 to 2-9) No. 1 resin composition containing no glass fiber
The first resin molded articles 10 of test examples 2-1 to 2-9 did not contain glass fibers. Furthermore, the resin composite molded bodies 1 of test examples 2-1 to 2-9 all had a bonding strength of 10MPa or more.
As can be seen from test examples 2-1 to 2-9, the invention according to the present embodiment can provide a resin composite molded article in which the strength at the time of bonding to another molded article can be further improved without being restricted by the presence or absence of an inorganic filler in the resin molded article and the color of the resin molded article.
Among them, in test examples 2-1, 2-2, 2-5, 2-8 and 2-9, the resin constituting the 1 st resin composition was the same as the resin constituting the 2 nd resin composition. Furthermore, the resin composite molded bodies 1 of test examples 2-1, 2-2, 2-5, 2-8 and 2-9 all had a bonding strength of 20MPa or more.
As can be seen from test examples 2-1, 2-2, 2-5, 2-8 and 2-9, in the invention described in this embodiment, the resin constituting the 1 st resin composition is preferably the same as the resin constituting the 2 nd resin composition.
(test examples 2-10 to 2-13) resin constituting the 1 st resin composition (resin constituting the 2 nd resin composition)
In test examples 2-10 to 2-13, the 1 st resin molded article 10 contained glass fibers. The resin constituting the 1 st resin composition is the same as the resin constituting the 2 nd resin composition. The resin composite molded bodies 1 of test examples 2-10 to 2-13 all had a bonding strength of 20MPa or more.
As can also be seen from test examples 2-10 to 2-13, in the invention according to the present embodiment, it is preferable that the resin constituting the 1 st resin composition is the same as the resin constituting the 2 nd resin composition.
(test examples 2-14 to 2-16) the difference (. DELTA.T) between the cylinder temperature in the 2-pass molding and the Vicat softening point of the 1 st resin composition was not less than 15 DEG C
In test examples 2-14 to 2-16, the 1 st resin molded article 10 contained glass fibers. The resin constituting the 1 st resin composition is different from the resin constituting the 2 nd resin composition, and the temperature in the injection step of the 2 nd resin composition is higher than the Vicat softening point of the 1 st resin composition by 15 ℃ or more.
The resin composite molded bodies 1 of test examples 2-14 to 2-16 all had a bonding strength of 10MPa or more.
(test examples 2-17 to 2-25) difference (. DELTA.T) between cylinder temperature in 2 passes of molding and Vicat softening point of the 1 st resin composition was <15 DEG C
In test examples 2-17 to 2-25, the 1 st resin molded article 10 contained glass fibers. The resin constituting the 1 st resin composition is different from the resin constituting the 2 nd resin composition, and the difference between the Vicat softening point of the 1 st resin composition and the temperature of the 2 nd resin composition in the injection step is less than 15 ℃.
In this case, even if the uncured 2 nd resin composition is injected onto the uneven surface 11 of the 1 st resin molded body 10, the uneven surface 11 of the 1 st resin molded body 10 is not thermally deformed, and the 1 st resin molded body 10 and the 2 nd resin molded body 20 cannot be appropriately joined. Therefore, the temperature in the injection step of the 2 nd resin composition needs to be higher than the Vicat softening point of the 1 st resin composition by 15 ℃ or more.
(test examples 2 to 26)
This test example is an example in which the 1 st resin composition is POM containing no glass fiber and the 2 nd resin composition is PEEK containing glass fiber. Δ T252, the bonding strength was 10.2 MPa.
< test example 3> the invention described in patent document 1
[ Table 3]
In table 3, the materials of the 1 st resin composition and the 2 nd resin composition are as follows.
POM: polyacetal resin (product name: DURACON M90-44, Vicat softening point: 148 ℃ C., product of Gei plastics Co., Ltd.)
POM containing glass fibers: polyacetal resin containing glass fiber (product name: DURACONGH-25, Vicat softening point: 154 ℃, manufactured by Georgi plastics Co., Ltd.)
PBT containing glass fiber: glass fiber-containing polybutylene terephthalate resin (product name: DURANEX3300, Vicat softening point: 214 ℃ C., product of Baoli plastics Co., Ltd.)
PPS containing glass fibers: polyphenylene sulfide resin containing glass fiber (product name: DURAFIDE PPS 1140A1, Vicat softening point: 266 ℃, manufactured by Georgi plastics Co., Ltd.)
[ invention described in patent document 1]
As a comparison with test example 2, a resin composite molded article 1 was obtained by the method described in patent document 1.
[ production of grooved resin molded article ]
The resin composition 1 described in Table 3 was injection-molded under the following conditions to obtain a plate-like injection-molded article having a longitudinal length of 13mm, a lateral length of 65mm and a thickness of 6.5mm, and then one side surface (longitudinal length of 6.5mm and lateral length of 13mm) formed in the thickness direction and the longitudinal direction of the injection-molded article was irradiated with a laser beam in a diagonal grid pattern 30 times so that the width of each groove was 100 μm and the interval between adjacent grooves was 300 μm. Using the oscillation wavelength: 1.064 μm, maximum rated output: the output of the 13W (average) laser was 90%, the frequency was 50kHz, and the scanning speed was 1000 mm/s. Thus, a grooved resin molded article was obtained.
(conditions for injection Molding of POM and POM containing glass fiber)
Preliminary drying: 80 ℃ for 3 hours
Barrel temperature: 200 deg.C
Temperature of the die: 80 deg.C
Injection speed: 16mm/sec
Pressure maintaining: 50MPa
(conditions for injection Molding of glass fiber-containing PBT)
Preliminary drying: 140 ℃ for 3 hours
Barrel temperature: 260 deg.C
Temperature of the die: 60 deg.C
Injection speed: 20mm/sec
Pressure maintaining: 50MPa
(conditions for injection Molding of PPS containing glass fiber)
Preliminary drying: 140 ℃ for 3 hours
Barrel temperature: 320 deg.C
Temperature of the die: 150 ℃ C
Injection speed: 20mm/sec
Pressure maintaining: 50MPa
[ production of resin composite molded article ]
Each grooved resin molded article was inserted into an injection molding die using a surface having grooves formed by laser irradiation as a contact surface, and the resin composition of table 2 shown in table 3 was injection molded under the same conditions as those described in [ production of grooved resin molded article ] of the invention described in patent document 1, to obtain a resin composite molded article.
[ evaluation ]
The joint strength of each of the resin composite molded articles 1 of test example 3 was measured by the same method as in test example 1. The results are shown in fig. 6. In fig. 6, the same examples (for example, test example 2-1 and test example 3-1) as those of test example 2 shown in table 2 were compared with each other in the same material combinations as those of test example 3.
[ test examples 3-1 to 3-4] No. 1 resin composition not containing glass fiber
In test examples 3-1 to 3-4, the grooved resin molded article did not contain glass fiber, and thus the resin composite molded article could not be obtained by the method described in patent document 1. On the other hand, as shown in test examples 2-1 to 2-4, by adopting the method described in the present embodiment, even if the 1 st resin molded article does not contain an inorganic filler, the resin composite molded article 1 having a bonding strength of 10MPa or more can be obtained.
[ test examples 3-5 to 3-8] resin constituting the 1 st resin composition (resin constituting the 2 nd resin composition)
By comparing test examples 3-5 to 3-8 with test examples 2-10 to 2-13, the bonding strength of the resin composite molded article obtained by the method of the present embodiment is equal to or higher than that of the resin composite molded article obtained by the method of patent document 1.
In addition, in the case of using the method described in patent document 1, in order to remove the resin component of the grooved resin molded product by irradiation with laser light to form the grooves, it is necessary to color the resin composition with a coloring agent such as carbon black so that the resin portion efficiently absorbs the laser light, and in contrast, in the invention described in the present embodiment, the uneven surface 11 is formed at the time point of injection molding of the 1 st resin molded product 10 by transfer of the unevenness provided in the mold, and therefore the color of the 1 st resin composition can be freely set without particular limitation, and is advantageous in view of being applicable to exterior parts and the like.
[ test examples 3-9 to 3-12] the difference (. DELTA.T) between the cylinder temperature at the time of molding the resin composite and the Vicat softening point of the 1 st resin composition was less than 15 DEG C
In test examples 3-9 to 3-12, the 1 st resin molded article 10 contained glass fibers. The resin constituting the 1 st resin composition is different from the resin constituting the 2 nd resin composition, and the difference between the cylinder temperature at the time of injection molding of the 2 nd resin composition and the Vicat softening point of the 1 st resin composition is less than 15 ℃.
In this case, as shown in test examples 2-19, 2-20, 2-24 and 2-25, sufficient bonding strength could not be obtained by the method of the present embodiment, while as shown in test examples 3-9 to 3-12, high bonding strength could be obtained by the method of patent document 1, and it can be said that the bonding mechanism was completely different between the method of the present embodiment and the method of patent document 1.
< test example 4> comparison between the shape of the uneven surface 11 and the resin material
Except for the shape of test example 1-2 (coefficient a (6L/bd)2) 38), a resin composite molded article 1 was molded in the same mold for injection molding as in test example 1 and under the same molding conditions as in test example 2 with the combinations of resin materials shown in table 5 for each of the shapes shown in table 4, and the bonding strength was measured by the same method as in test example 1. The results are shown in table 5.
[ Table 4]
| Shape 1 | |
Shape 3 | Shape 4 | Shape 5 | Shape 6 | |
| Height L (mm) of |
0.4 | 0.8 | 0.4 | 0.8 | 0.8 | 1 |
| Width d (mm) of |
0.4 | 0.4 | 0.3 | 0.3 | 0.2 | 0.2 |
| Width b (mm) of |
0.4 | 0.4 | 0.3 | 0.3 | 0.2 | 0.2 |
| Coefficient a | 38 | 75 | 89 | 178 | 600 | 750 |
Here, shape 1 in Table 4 is the same as that of test example 1-2.
[ Table 5]
As shown in test examples 4-1 to 4-4 and 4-7, it was confirmed that the coefficient a (6L/bd)2) When the value of (A) is 5 to 600 inclusive, and the difference (Delta T) between the Vicat softening point of the 1 st resin composition and the temperature of the 2 nd resin composition in the injection step is in the range of 15 to 300 ℃, a high bonding strength of 10MPa or more can be obtained. Further, as shown in test examples 4-5 and X-6, it was confirmed that in the case where the difference between the temperature of the injection step of the 2 nd resin composition and the Vicat softening point of the 1 st resin composition is less than 15 ℃, only the bonding strength of less than 10MPa was obtained in all the coefficients a. In addition, in test examples 4 to 7, the phrase "impossible to manufacture" with a being 750 means that the convex portion 13 of the shape 6 is very slender and the mold manufacturing is difficult, so that the test cannot be performed.
< test example 5> examination of method for evaluating coefficient a
Coefficient a is 6L/bd2Is the size of the mold. On the other hand, the resin composite molded article is welded at the joining interface, and therefore the shape of the joining interface between the 1 st resin molded article 10 and the 2 nd resin molded article 20 in the resin composite molded article 1 is not necessarily exactly the same as the size of the mold.
However, in the case of examining whether or not the resin composite molded article is in the technical range of the patent invention, it is difficult to prove whether or not the resin composite molded article is in the technical range of the patent invention according to the size of the mold, and therefore, it is necessary to determine a method of proving whether or not the resin composite molded article is in the technical range of the patent invention according to the shape of the resin composite molded article 1.
The method of evaluating the coefficient a from the resin composite molded article 1 may include the following methods: (1) evaluation by X-ray CT; (2) dissolving the 2 nd resin molded body 20 using a solvent which does not dissolve the 1 st resin molded body 10 but dissolves the 2 nd resin molded body 20, and evaluating the coefficient a for the remaining 1 st resin molded body 10; (3) the resin composite molded article 1 is cut so that the boundary between the 1 st resin molded article 10 and the 2 nd resin molded article 20 can be observed, and the boundary between the 1 st resin molded article 10 and the 2 nd resin molded article 20 is observed from the cut cross section. Among them, from the viewpoint of being able to evaluate the coefficient a simply and at low cost, it is preferable that the coefficient a be evaluated by the method (3) in which the resin composite molded body 1 is cut so that the boundary between the 1 st resin molded body 10 and the 2 nd resin molded body 20 can be observed, and the boundary between the 1 st resin molded body 10 and the 2 nd resin molded body 20 is observed from a cross section after cutting.
Therefore, as a method for evaluating the coefficient a, it is considered whether the method (3) can be employed.
(discussing)
The resin composite molded article 1 of test examples 1 to 3 was cut downward from above so that the boundary between the 1 st resin molded article 10 and the 2 nd resin molded article 20 could be observed. Then, the boundary between the 1 st resin molded body 10 and the 2 nd resin molded body 20 is enlarged from the cut cross section and observed. The results are shown in fig. 7.
As shown in fig. 7, the cross-sectional shape of the resin composite molded article 1 is slightly different from the shape of the mold. This is presumably because the resin composite molded article 1 is welded at the joint interface.
However, as shown in fig. 7, the size of the joining interface does not greatly vary before and after joining, and the coefficient a can be accurately evaluated by the method (3) described above.
Therefore, in the present embodiment, the method of evaluating the coefficient a is to adopt the method (3) described above: the resin composite molded article 1 is cut so that the boundary between the 1 st resin molded article 10 and the 2 nd resin molded article 20 can be observed, and the boundary between the 1 st resin molded article 10 and the 2 nd resin molded article 20 is observed from the cut cross section.
< test example 6> examination of the Effect of Molding conditions
In general, when joining resin molded bodies by insert molding, attempts have been made to improve the joining strength under molding conditions such as: setting the molding conditions such as the temperature of the charging barrel, the temperature of the mold, the injection speed, the pressure maintaining pressure and the like to be higher when molding is carried out for 2 times; the 1 st molded article (the 1 st resin molded article 10) was preliminarily heated. Therefore, in the present embodiment, the molding conditions were changed in a state where the shape (coefficient a) of the uneven surface 11 and the combination (Δ T) of the resin materials were matched, and the influence of the molding conditions on the joining strength was examined.
[1 time formation ]
Polyphenylene sulfide resin (product name: DURAFIDE 1140A1, Vicat softening point: 266 ℃ C., product of Corp. Plastic Co., Ltd.) was injection-molded under the following conditions, and a coefficient a (6L/bd) similar to that of shape 2 of test example 4 was obtained2) 75 of the 1 st resin molded article 10.
(conditions of 1-time Molding)
Preliminary drying: 140 ℃ for 3 hours
Barrel temperature: 320 deg.C
Temperature of the die: 150 ℃ C
Injection speed: 20mm/sec
Pressure maintaining: 50MPa
[2 formation ]
A polyacetal resin (product name: DURACON M90-44, Vicat softening point: 148 ℃ C., product name: Takara Shuzo Co., Ltd.) was injection-molded under the molding conditions shown in Table 6 by inserting the uneven surface 11 of the first resin molded article 10 as a contact surface into the same injection-molding mold as in test example 1 to obtain a resin composite molded article 1. Here, the molding conditions of test example 6-1 were the same as those of the glass fiber-containing POM of test example 2, and the respective items of the molding conditions were changed based on this. In the table, "preliminary heating" means that the 1 st resin molded article 10 is left to stand on a heating plate at 150 ℃ until the surface temperature of the contact surface rises to 150 ℃, and then is fitted into a mold for injection molding.
[ evaluation ]
The joint strength was measured for each resin composite molded article 1 of test example 6 by the same method as in test example 1. The results are shown in table 6.
[ Table 6]
| Test examples | Preliminary drying | Temperature of the barrel | Temperature of the mold | Speed of injection | Pressure maintaining pressure | Preheating | Bonding strength |
| 6-1 | 80 ℃ for 3 hours | 200℃ | 80℃ | 16mm/sec | 50MPa | Is free of | 3.8MPa |
| 6-2 | 80 ℃ for 3 hours | 200℃ | 120℃ | 16mm/sec | 50MPa | Is free of | 4.2MPa |
| 6-3 | 80 ℃ for 3 hours | 200℃ | 80℃ | 50mm/sec | 50MPa | Is free of | 4.4MPa |
| 6-4 | 80 ℃ for 3 hours | 200℃ | 80℃ | 16mm/sec | 50MPa | Comprising (150 degree C) | 3.9MPa |
| 6-5 | 80 ℃ for 3 hours | 200℃ | 120℃ | 50mm/sec | 50MPa | Is free of | 3.9MPa |
| 6-6 | 80 ℃ for 3 hours | 200℃ | 120℃ | 16mm/sec | 50MPa | Comprising (150 degree C) | 4.6MPa |
| 6-7 | 80 ℃ for 3 hours | 200℃ | 120℃ | 50mm/sec | 50MPa | Comprising (150 degree C) | 3.9MPa |
| 6-8 | 80 ℃ for 3 hours | 220℃ | 120℃ | 50mm/sec | 100MPa | Comprising (150 degree C) | 3.8MPa |
According to the results of test example 6 shown in table 6, the change in the bonding strength was about 0.8MPa at most when various molding conditions were changed. It was confirmed that the bonding strength of test example 6-1 obtained by the same combination of resin materials (PPS containing glass fibers as the resin composition 1, POM as the resin composition 2) and the same molding conditions as those of test examples 2-24 was improved by 1MPa or more as compared with that of test example 2-24. That is, the improvement of the bonding strength by the shape (coefficient a) of the uneven surface 11 of the present embodiment can obtain a better effect than the improvement of the bonding strength by the molding conditions.
Description of the reference numerals
1. A resin composite molded body; 10. 1 st resin molded body; 11. a concave-convex surface; 12. a recess (groove); 13. a convex portion (mountain); 20. and (2) a resin molded article.
Claims (9)
1. A method for producing a resin composite molded article, wherein,
the method for producing a resin composite molded article comprises an injection step of injecting a thermoplastic or thermosetting 2 nd resin composition into a surface of a1 st resin molded article composed of a cured product of a1 st resin composition which is thermoplastic and does not contain a coloring agent for absorbing laser light and having irregularities formed by injection molding on the surface, wherein the 1 st resin molded article and the 2 nd resin molded article composed of a cured product of the 2 nd resin composition are joined to each other,
in the method for producing a resin composite molded article,
a value obtained by subtracting the Vicat softening point of the 1 st resin molded body from the temperature of the 2 nd resin composition in the injection step is 15 ℃ to 300 ℃,
in the resin composite molded article, when the height of the convex portion of the unevenness of the 1 st resin molded article is represented by L, the width of the convex portion in the direction parallel to the direction in which the 2 nd resin composition is injected is represented by d, and the width of the convex portion in the direction perpendicular to the direction in which the 2 nd resin composition is injected is represented by b, 6L/bd2The value of (A) is 5 to 600 inclusive, wherein the units of L, d and b are mm.
2. The method for producing a resin composite molded body according to claim 1,
the value obtained by subtracting the Vicat softening point of the 1 st resin molded body from the temperature of the 2 nd resin composition in the injection step is 30 ℃ to 110 ℃.
3. The method for producing a resin composite molded body according to claim 1,
the 1 st resin composition is a resin composition containing no inorganic filler.
4. The method for manufacturing a resin composite molded body according to claim 2,
the 1 st resin composition is a resin composition containing no inorganic filler.
5. The method for producing the resin composite molded body according to any one of claims 1 to 4, wherein the resin constituting the 1 st resin composition is the same as the resin constituting the 2 nd resin composition.
6. The method for producing a resin composite molded article according to any one of claims 1 to 4, wherein the resin constituting the 1 st resin composition is different from the resin constituting the 2 nd resin composition.
7. The method for producing a resin composite molded article according to any one of claims 1 to 4,
when the interval between adjacent convex portions of the 1 st resin composition is represented by P and the groove width of the concave portion is represented by W, the value of P is 1.5W to 4W, wherein the unit of P, W is mm.
8. The method for manufacturing a resin composite molded body according to claim 5,
when the interval between adjacent convex portions of the 1 st resin composition is represented by P and the groove width of the concave portion is represented by W, the value of P is 1.5W to 4W, wherein the unit of P, W is mm.
9. The method for manufacturing a resin composite molded body according to claim 6,
when the interval between adjacent convex portions of the 1 st resin composition is represented by P and the groove width of the concave portion is represented by W, the value of P is 1.5W to 4W, wherein the unit of P, W is mm.
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| JP5632567B1 (en) * | 2013-02-12 | 2014-11-26 | ポリプラスチックス株式会社 | Grooved resin molded product |
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