JP6241446B2 - Resin member and vehicle body structure including this member - Google Patents

Description

  The present invention relates to a resin member, particularly a vehicle resin member, and a vehicle body structure including the member.

  Resin members made of resin are often used as constituent materials in various daily fields such as vehicle members, optical members, and building members from the viewpoint of recent weight saving and energy saving.

  For example, in the case of a vehicle member, conventionally, the use of a resin window member has been studied. The resin window member is fixed to the vehicle body via an adhesive layer at an end thereof (for example, Patent Document 1).

  Specifically, an example of the rear window 100 in the prior art is shown in FIGS. 6A is a schematic overall view when the rear window of the automobile is viewed from the outside of the vehicle, and FIG. 6B is a schematic cross-sectional view when the AA cross section in FIG. 6A is viewed in the direction of the arrow. 6C is a partially enlarged cross-sectional view of the end portion of the rear window when the BB cross section in FIG. 6A is viewed in the direction of the arrow, and the rear window is fixed to the vehicle body. It is sectional drawing which shows a state. As shown in FIGS. 6A to 6C, the rear window 100 usually has an annular black resin layer 102 formed at the end thereof, and an adhesive layer 103 formed on the surface of the black resin layer 102. The rear window 100 is fixed to the vehicle body 105. The presence of the black resin layer 102 prevents see-through of the adhesive layer 103 and the vehicle body 105 from the outside of the vehicle and improves the appearance quality.

Special table 2014-502229 gazette

  However, if the rear window 100 is simply fixed by the adhesive layer 103 as described above, vibration due to outside noise such as running noise due to contact between the tire and the road cannot be sufficiently blocked, and there is a problem in sound insulation. was there.

  The present invention provides a resin member, particularly a vehicle resin member, and a vehicle body structure provided with the resin member, which has excellent adhesion to other members such as a vehicle body and has sufficiently good sound insulation. For the purpose.

The present invention
A resin member including a resin base material and an adhesive layer for fixing the resin base material to another member,
Resin member in which the width b (mm) and height h (mm) of the adhesive layer, the storage elastic modulus (Young's modulus) E (MPa), and the loss factor tan δ of the adhesive constituting the adhesive layer satisfy the following relational expression In particular, the present invention relates to a vehicle resin member and a vehicle body structure including the resin member.
0.03 ≦ tan δ × (h / Eb)

  The resin member of the present invention is sufficiently excellent in sound insulation while having good adhesion to other members such as a vehicle body.

(A) is a schematic whole outline view when an example of the window member for vehicles of the present invention is seen from the outside of a car, and (B) is a schematic sectional view when the AA section in (A) is seen in the direction of an arrow. And (C) is a partially enlarged cross-sectional view of the end portion of the vehicle window member when the BB cross section in (A) is viewed in the direction of the arrow, and the vehicle window member is fixed to the vehicle body. FIG. (A) is a schematic whole outline view when another example of the window member for vehicles of the present invention is seen from the outside of a vehicle, and (B) is a schematic cross section when the AA section in (A) is seen in the direction of an arrow. It is a figure, (C) is a partially expanded sectional view of the edge part of the window member for vehicles when the BB section in (A) is seen in the direction of an arrow, and the window member for vehicles is fixed to the body. It is sectional drawing which shows the state which carried out. The top plan view and schematic sectional view of the sample used in the sound insulation test conducted in the examples are shown. The schematic block diagram of the apparatus for performing a sound insulation test is shown. The top plan view and schematic sectional view of the sample used in the adhesion test conducted in the examples are shown. (A) is a schematic outline drawing of the rear window 100 when the conventional rear window of the automobile is viewed from the outside of the vehicle, and (B) is a schematic sectional view when the AA cross section in (A) is viewed in the direction of the arrow. (C) is a partially enlarged cross-sectional view of the end portion of the rear window when the BB cross section in (A) is viewed in the direction of the arrow, and shows a state in which the rear window is fixed to the vehicle body FIG.

  The resin member of the present invention includes a resin base material and an adhesive layer, and is fixed to another member via the adhesive layer. Hereinafter, the case where the resin member of the present invention is used for a vehicle will be described in detail with reference to FIGS. 1 to 2, but it is obvious that the effects of the present invention can be obtained even for optical or architectural use. Unless otherwise specified, the same reference numerals in FIGS. 1 to 2 mean the same members except that the shapes are different.

  FIG. 1A is a schematic overall view of an example of a vehicle window member among vehicle resin members. FIG. 1B is a schematic cross-sectional view of the AA cross section in FIG. 1C is a partially enlarged cross-sectional view of the end portion of the vehicle window member when the BB cross section in FIG. 1A is viewed in the direction of the arrow, and the vehicle window member is another member. It is sectional drawing which shows the state fixed to the vehicle body as.

  In the present invention, from the viewpoint of appearance quality, it is preferable that the colored resin layer 2 is formed between the resin base material 1 and the adhesive layer 3 as shown in FIG. That doesn't mean it doesn't happen.

The resin constituting the resin substrate 1 may be any thermoplastic polymer or thermosetting polymer, and a thermoplastic polymer is usually used from the viewpoint of moldability. As the thermoplastic polymer, any polymer having thermoplasticity can be used. Examples include the following polymers and mixtures thereof:
Polyolefin resins such as polyethylene and polypropylene, and modified products thereof;
Polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polylactic acid (PLA);
Polyacrylate resins such as polymethyl methacrylate resin (PMMA);
Polyether resins such as polyether ether ketone (PEEK) and polyphenylene ether (PPE);
Polyacetal (POM);
Polyphenylene sulfide (PPS);
PA6, PA66, PA11, PA12, PA6T, PA9T, MXD6 and other polyamide-based resins (PA);
Polycarbonate resin (PC);
Polyurethane resin;
A fluoropolymer resin; and a liquid crystal polymer (LCP).

Any polymer having thermosetting properties can be used as the thermosetting polymer. Examples include the following polymers and mixtures thereof:
Phenolic resin;
Epoxy resin;
Melamine resin;
Urea resin.

  As the resin base 1, a transparent resin base is used particularly when a resin member is used as a vehicle window member. As the resin constituting the transparent resin base material, a transparent polymer such as a polycarbonate-based resin is used among the above polymers.

  The resin base material 1 may contain any additive. Examples of such additives include colorants and antioxidants. In particular, when the resin member is used as a vehicle window member, the transparent resin base material does not contain a colorant.

  The thickness (T1) of the resin base material 1 is not particularly limited, and is usually 1 to 20 mm, preferably 2 to 15 mm, more preferably 3 to 10 mm, and particularly when the resin member is used as a vehicle window member. Is most preferably 3 to 9 mm, particularly 3 to 5 mm.

  As shown in FIGS. 1A to 1C, the colored resin layer 2 is usually formed at the peripheral end portion on one surface of the resin base material 1, and as a result, has a ring shape as a whole.

  As the resin constituting the colored resin layer 2, the same resin as that constituting the resin base material 1 can be used, and a thermoplastic polymer is usually used from the viewpoint of moldability. Examples of the thermoplastic polymer include the same polymers as in the resin substrate 1 and mixtures thereof.

  As the colored resin layer 2, particularly when a resin member is used as a vehicle window member, a black resin layer is preferably used. By forming the adhesive layer 3 on the surface of the colored resin layer and fixing the vehicle window member, it is possible to prevent the adhesive layer from being seen through from the outside of the vehicle. Of the above-mentioned polymers, polycarbonate resins, polyester resins, and mixtures thereof are preferably used as the resin constituting the colored resin layer.

  The colored resin layer 2 may contain any additive. As such an additive, the same additive as in the resin base material 1 is mentioned. In particular, when the resin member is used as a vehicle window member, the colored resin layer 2 contains at least a colorant as an additive. A colorant such as a black colorant is used as the colorant. Examples of the black colorant include carbon black.

  The thickness (T2) of the colored resin layer 2 is not particularly limited, and is usually 1 to 20 mm, preferably 2 to 15 mm, more preferably 2 to 10 mm, and particularly when the resin member is used as a vehicle window member. Is most preferably 2 to 4 mm.

  The adhesive layer 3 is for fixing the resin base material 1 to another member. In particular, when the resin member 10 is used as a vehicle window member, the other member is a vehicle body.

  The adhesive layer 3 is formed on the surface of the colored resin layer 2, and as a result, like the colored resin layer 2 formed on the peripheral end portion of the resin base material 1, has an annular shape as a whole. In FIG. 1 (A), the adhesive layer 3 is usually not visible due to the presence of the colored resin layer 2 and is therefore indicated by a broken line.

The adhesive layer 3 has a width b (mm) and a height h (mm) as well as a storage elastic modulus (Young's modulus) E (MPa) and a loss coefficient tan δ of the adhesive constituting the adhesive layer. It is preferable to satisfy I), in particular, relational expression (II) and to satisfy relational expression (III) from the viewpoint of further improving sound insulation and adhesiveness.
0.03 ≦ tan δ × (h / Eb) (I)
0.03 ≦ tan δ × (h / Eb) ≦ 2 (II)
0.1 ≦ tan δ × (h / Eb) ≦ 1 (III)

  “Tan δ × (h / Eb)” is a product of the loss coefficient tan δ and “h / Eb”. By setting such a product within the above range, vibration based on noise can be attenuated, so that sound insulation can be sufficiently improved. If the product is less than 0.03, sufficient sound insulation cannot be obtained.

  “H / Eb” is usually 0.1 to 3.5, and preferably 0.3 to 3.2 from the viewpoint of further improving sound insulation.

  “H” is the height (mm) of the adhesive layer 3, and is the height (thickness) of the adhesive layer when the resin member is bonded and fixed to another member. The height h (mm) of the adhesive layer 3 is usually 0.5 × T1 to 2.0 × T1, and preferably 1 × T1 to 1.5 × T1 from the viewpoint of further improving the sound insulation. When the height h is too large, the adhesiveness is lowered. T1 is the thickness (mm) of the resin substrate 1. If the height h is too small, the sound insulation performance decreases.

  As the height h of the adhesive layer 3, an average value of the heights at arbitrary 100 locations in the adhesive layer 3 is used.

  “B” is the width (mm) of the adhesive layer 3, and is the width of the adhesive layer when the resin member is bonded and fixed to another member. Specifically, “b” is a width in a cross section perpendicular to the traveling direction of the adhesive layer. The width b (mm) of the adhesive layer 3 is usually 0.5 × T1 to 2.5 × T1, and preferably 0.5 × T1 to 2 × T1 from the viewpoint of further improving sound insulation. If the width b is too large, the sound insulating property of the resin base material 1 is lowered. When the width b is too small, the adhesiveness is lowered.

  The width b of the adhesive layer 3 is an average value of the widths of arbitrary 100 linear portions in the adhesive layer 3. As long as the adhesive layer 3 has an annular shape, the present invention does not prevent the adhesive layer 3 from having a width outside the above range at the corner portion P as shown in FIG.

  “E” is the storage elastic modulus (Young's modulus) of the adhesive constituting the adhesive layer 3, and is the storage elastic modulus after the adhesive is solidified (cured). E is usually 0.1 MPa or more, particularly 0.1 to 100 MPa, preferably 0.1 to 10 MPa, and more preferably 0.2 to 8 MPa for further improvement of sound insulation and adhesiveness.

  The storage elastic modulus of the adhesive is a value measured by MAX-R2KN (manufactured by Japan Measurement System) at an ambient temperature of 23 ° C. For the test piece, an adhesive was placed on a steel plate that had been subjected to a release treatment or a glass plate that had been subjected to the same treatment so that bubbles would not enter. After placing a glass plate and placing a spacer to produce a sheet having a thickness of 2.8 ± 0.2 mm and curing it, JIS K 6251 4. The same dumbbell-shaped No. 2 was used.

  “Tan δ” is a loss factor of the adhesive, and is a loss factor after the adhesive is solidified (cured). tan δ is usually 0.1 or more, particularly 0.1 to 1, and preferably 0.2 to 0.5 from the viewpoint of further improving the sound insulation.

  The loss factor tan δ of the adhesive is a value measured by RS6000 (manufactured by Eihiro Seiki) at an ambient temperature of 23 ° C., a frequency of 10 Hz, and a gripping tool spacing of 20 mm. For the test piece, an adhesive was placed on a steel plate that had been subjected to a release treatment or a glass plate that had been subjected to the same treatment so that bubbles would not enter. A glass plate was placed, a spacer was placed, a 2.8 ± 0.2 mm thick sheet was produced and cured, and then punched out into a shape having a width of 10 mm and a length of 60 mm.

  In the present invention, “h / b” is a coefficient relating to the cross-sectional shape of the adhesive layer, and the value increases as the height with respect to the width of the adhesive layer increases. h / b is preferably 0.5 to 3, more preferably 0.6 to 2.6, from the viewpoint of further improving sound insulation.

  In the present invention, “tan δ / E” is preferably 0.01 to 2 and more preferably 0.04 to 0.8 from the viewpoint of further improving the sound insulation.

  The present invention is based on the finding that the larger the ζ (r) is, the higher the sound insulation of the window tends to be.

η (r): loss factor of the entire structural system V (r): strain energy of the entire structural system Vv (r): strain energy of the adhesive ηv (r): loss factor of the adhesive (tan δ)
Vw (r): Strain energy ηw (r) of the window material: Loss coefficient ζ (r) of the window material: Damping ratio of the entire structural system

  In order to increase ζ (r), it is better that ηv (= tan δ) and Vv are larger.

  The strain energy when considered as a bar is the following formula.

h: Total length (adhesive application height)
N: Axial force acting on the adhesive M: Bending moment acting on the adhesive Q: Shearing force acting on the adhesive E: Elastic modulus (Young's modulus) of the adhesive
A: Cross-sectional area of the adhesive I: Secondary moment of inertia of the adhesive G: Shear elastic modulus of the adhesive k: Shape factor of the adhesive

b: Adhesive application width dx: Adhesive application length element v: Adhesive Poisson's ratio Eall: Elastic modulus of the entire structural system Ew: Elastic modulus of window material

Therefore, in order to increase Vv, it is better that h / Eb is larger.
Therefore, in order to increase ζ (r), the larger tan δ · h / Eb, the better.

  The adhesive layer 3 is formed as one annular loop in FIGS. 1A to 1C, but may be formed as a plurality of annular loops. For example, in FIGS. 2A to 2C, the adhesive layer is formed as two annular loops (3A and 3B).

  When the adhesive layer is formed as a large number of annular loops, the sum of the widths of the adhesive layers may be set as the width b to satisfy the above relational expression and the prescribed range of b. For example, as shown in FIGS. 2A to 2C, when the widths of the adhesive layers 3A and 3b are b1 (mm) and b2 (mm), respectively, the value of b1 + b2 is the width b and the above relationship It suffices to satisfy the formula and the prescribed range of b.

  When the adhesive layer is formed as a large number of annular loops, the gap (interval) between the adhesive layers, for example, the length c shown in FIG. 2C is usually 1.5 × T1 to 4 × T1. From the viewpoint of further improving the sound insulation, it is preferably 2 × T1 to 3 × T1. T1 is the thickness (mm) of the resin substrate 1.

  As the adhesive constituting the adhesive layer 3, any adhesive that is used for bonding and fixing automobile parts such as windows and interior panels in the automobile industry can be used. Examples of such adhesives include urethane adhesives, synthetic rubber adhesives, and acrylic adhesives.

  The urethane adhesive contains a urethane prepolymer and an organic tin compound. From the viewpoint of adhesiveness, the urethane prepolymer is prepared by adding a diisocyanate compound, particularly 4,4′-diphenylmethane diisocyanate, to a mixture of a polyether triol having a number average molecular weight of 1000 or more and 7000 or less and a polyether diol, an isocyanate group and a hydroxyl group. Are preferably obtained by reacting within a range of 1.1 to 2.5. The organic tin compound is a compound that catalyzes the reaction between an isocyanate group and active hydrogen, and is not particularly limited as long as it is a compound having an organic group.

  It is preferable that a urethane type adhesive contains an adhesion imparting agent from a viewpoint of the further improvement of adhesiveness. The adhesion-imparting agent is, for example, an isocyanate silane compound that is a reaction product of 3- (N-phenyl) aminopropyltrimethoxysilane and a biuret of hexamethylene diisocyanate. This adhesion-imparting agent comprises 3- (N-phenyl) aminopropyltrimethoxysilane and a biuret of HDI having an isocyanate group / amino group (NCO group / NH group) of 1.5 / 1.0 or more and 9.0. It is obtained by adding within the range of /1.0 or less.

  The urethane-based adhesive can impart adhesiveness by being cured by moisture at room temperature.

  The synthetic rubber adhesive includes a synthetic rubber, a vulcanizing agent, and a foaming agent. The synthetic rubber preferably contains uncrosslinked synthetic rubber such as butadiene rubber and / or partially crosslinked synthetic rubber such as styrene-butadiene copolymer rubber from the viewpoint of adhesiveness. The vulcanizing agent preferably contains a quinonedioxime vulcanizing agent. Examples of the foaming agent include thermally decomposable organic foaming agents such as azodicarbonamide, N, N′-dinitrosopentamethylenetetramine, and 4,4′-oxybis (benzenesulfonylhydrazide).

  The synthetic rubber-based adhesive can impart adhesiveness by being cured by heating.

The acrylic adhesive is obtained by blending a thermosetting material with an acrylic sol in which acrylic resin particles having a gradient structure and a filler are dispersed in a plasticizer. Acrylic resin particles having a gradient type structure are acrylic resin particles in which the ratio of constituent monomers is changed in a multistage manner or continuously from the core portion to the shell portion. As a thermosetting material, it is preferable to mix | blend the block-ized urethane prepolymer which blocked the free isocyanate group of the terminal isocyanate group containing urethane prepolymer, and its latent hardener from an adhesive viewpoint. The latent curing agent may be any compound that can be activated at a temperature of 60 ° C. or more and can react with an isocyanate group. For example, an aliphatic polyamine and an amine or aromatic having a cyclic structure having at least one NH ₂ or NH group. It is preferably a reaction product of a group polyamine and a diisocyanate compound.

  The acrylic adhesive can impart adhesiveness by being cured by heating.

  The surface of the colored resin layer 2 on which the adhesive layer 3 is formed (or the surface of the resin base material 1 when the colored resin layer 2 is not formed) is preferably provided with a concavo-convex structure from the viewpoint of adhesiveness. . By providing the concavo-convex structure, the contact area with the adhesive layer is increased, so that the adhesion is further improved.

  The concavo-convex structure includes a roughened structure (a fine concavo-convex in micrometer units) formed by roughening the surface, a relatively large concavo-convex structure having a convex part and / or a concave part on the surface, and a composite structure thereof. However, a roughened structure is preferable from the viewpoint of further improving the adhesiveness. When the surface on which the adhesive layer 3 is formed has a roughened structure, the height h of the adhesive layer 3 is the height from the surface having the roughened structure. When the surface on which the adhesive layer 3 is formed has a relatively large uneven structure, the height h of the adhesive layer 3 is an average height of the minimum thickness from the convex portion and the maximum thickness from the concave portion.

  The roughened structure can be imparted to the surface of the colored resin layer or the resin base material by transferring the roughness of the mold surface at the time of molding or polishing after the molding. The surface roughness Ra of the surface provided with the roughened structure is usually 0.05 to 35 μm, preferably 0.2 to 10 μm.

  As a relatively large concavo-convex structure, a mountain-valley structure in which peaks and valleys are alternately and continuously formed, a polygonal pyramid, a polygonal frustum, a cone, a truncated cone, a polygonal column, a cylinder, and / or a hemisphere Convex structure with convex part, polygonal cone hole, polygonal frustum hole, conical hole, frustoconical hole, polygonal columnar hole, cylindrical hole and / or hemispherical hole (dimple) concave Or a concave structure formed in the above structure.

  The height of the convex portion and the depth of the concave portion in a relatively large concavo-convex structure are usually 0.05 μm to 2 mm, preferably 0.2 μm to 1 mm.

  The resin member of the present invention can be manufactured by forming the colored resin layer 2 and the adhesive layer 3 in order after forming the resin substrate 1.

  Any method may be employed as the method for forming the resin substrate 1 and the method for forming the colored resin layer 2 as long as they can be molded into a predetermined shape. The resin base material 1 and the colored resin layer 2 are independently molded using, for example, an injection molding method, a press molding method, or the like using a mold processed into a predetermined shape.

  A preferable method for producing the resin base material 1 and the colored resin layer 2 from the viewpoint of moldability is a method in which the resin layer 2 is formed by an injection molding method after the resin base material 1 is formed by an injection molding method.

  The adhesive layer 3 can be formed by pressing the applied adhesive against another member such as a vehicle body and solidifying the adhesive with a predetermined cross-sectional shape. Solidification may be simple solidification or curing by moisture or heat depending on the type of adhesive.

  The resin member of the present invention is useful as a vehicle member, an optical member, a building member, or the like.

  Examples of the vehicle member include vehicle window members such as a roof window, a front window, a triangular window, a rear window, a rear quarter window, and a back window, and interior parts such as an interior panel.

  When the resin member of the present invention is used as a vehicle window member (for example, a rear window), the resin base material 1 is the transparent resin base material, and the colored resin layer 2 is the black resin layer.

[Example 1]
(Manufacture of sound insulation test samples)
A sample 20 shown in FIG. 3 was manufactured. FIG. 3 shows a top plan view of the sample 20 and a schematic sectional view thereof. In FIG. 3, the sample 20 was specifically manufactured by fixing the resin base material 21 to the holding plate (steel plate) 25 having the opening 26 via the adhesive layer 22. The dimensions of each member were as shown in FIG.

  The resin substrate 21 is a polycarbonate flat plate.

  The application shape (cross-sectional shape) of the adhesive layer 22 is 4 mm wide × 5 mm high. The adhesive layer 22 is obtained by applying a urethane-based adhesive (adhesive A) manufactured by a method described later and solidifying sufficiently.

  In the manufacture of the sample 20, a black resin layer (not shown) was formed between the resin base material 21 and the adhesive layer 22. Specifically, a mixed polymer of polycarbonate and polyethylene terephthalate and carbon black were melted and mixed, applied to the peripheral edge of the resin base material 21, and cooled to form an annular black resin layer (thickness 3 mm). The surface roughness Ra of the surface of the black resin layer on which the adhesive layer 22 is formed was a value described in Table 1.

(Manufacture of urethane adhesive: Adhesive A)
A plasticizer, carbon black, calcium carbonate, and morpholine catalyst were added to the urethane prepolymer in the amounts shown below, and mixed for 1 hour using a mixer under vacuum to obtain a preliminary composition.
-100 parts by weight of urethane prepolymer;
Plasticizer: 20 parts by weight of diisononyl phthalate (DINP) (Mitsubishi Chemical Corporation);
Carbon black; 50 parts by weight of Elftec 8 (Cabot)
・ Calcium carbonate; heavy calcium carbonate (trade name “SB Blue”, manufactured by Shiraishi Calcium Co., Ltd.) 40 parts by weight;
-Morpholine-based catalyst; U-CAT (660M, manufactured by San Apro) 0.8 parts by weight;

Each component of the amount shown below was mix | blended with respect to the preliminary composition, and these were mixed uniformly and the urethane type adhesive agent was produced.
-Adhesive agent A 6 parts by weight;
Organic tin catalyst: Neostan U-810 (manufactured by Nitto Kasei Kogyo Co., Ltd.) 0.01 parts by weight.

The urethane prepolymer is synthesized by the following method.
750 g of polyoxypropylene triol (trade name: Exenol 5030, number average molecular weight of about 5000, manufactured by Asahi Glass Co., Ltd.), which is a polyether triol, and polyoxypropylene diol (trade name: Exenol 2020, number of about 2000), which is a polyether diol. , Manufactured by Asahi Glass Co., Ltd.) at a mass ratio of 70/30, the mixture was dehydrated at 120 ° C. under reduced pressure, and then melted 4,4′-diphenylmethane diisocyanate (trade name: Isonate 125M, manufactured by Mitsui Takeda Urethane Co., Ltd.) 4 The amount of NCO group of 4,4'-diphenylmethane diisocyanate and the OH group of the above mixture was 1.7 so that the urethane prepolymer was obtained after mixing and stirring at 80 ° C. for 24 hours during nitrogen substitution. The NCO group content of the obtained urethane prepolymer was 1.1% by mass in the total amount of the urethane prepolymer.

The adhesion-imparting agent A is synthesized by the following method.
While stirring 100 g of hexamethylene diisocyanate (HDI) biuret (trade name: D165N, NCO group: 23.4% by mass, Takeda Pharmaceutical Co., Ltd.), NCO group / NH group was 3/1 in N ₂ stream. In this way, 26 g of 3- (N-phenyl) aminopropyltrimethoxysilane (trade name: Y9669, manufactured by Nihon Unicar Co., Ltd.) was reacted while being dropped onto a biuret body of HDI, whereby an adhesion-imparting agent A (average molecular weight: 720 , NCO group: 12.1% by mass).

  When a urethane adhesive was used, solidification for sample production was performed by allowing the sample to stand for 168 hours in an atmosphere of 20 ° C. ± 2 ° C. and 60 RH% ± 10 RH%.

(Sound insulation test: sound transmission loss)
A sound insulation test was performed using the apparatus shown in FIG. Specifically, the reverberation room 301 is used as the sound source room, and the anechoic room 302 is used as the sound receiving room. The sound power incident on the sample 20 necessary for the measurement of the sound transmission loss measures the average sound pressure level in the reverberation chamber, and the sound power transmitted through the sample 20 measures the sound intensity in the direction transmitted through the opening 26 in the anechoic chamber. To get by. The sample 20 is installed so that the resin base material 21 is disposed on the reverberation chamber 301 side and the holding plate 25 is disposed on the anechoic chamber 302 side. 4, 303 is a speaker, 304 is a microphone, 305 is a microphone rotator, 306 is an intensity probe, 307 is a microphone traverse, 310 is a microphone amplifier, 311 is an equalizer power amplifier, 312 is an audio interface, 313 is a microphone moving device Indicates a controller.
Measurement method: Sound transmission loss is measured by a sound intensity method (ISO 15186-1, JIS A1441-1) in a small reverberation room-an anechoic room.
・ Measurement frequency band: 1 kHz.
Sample opening surface: 500 mm × 500 mm = 0.25 m ² .
-Incident power: Calculated from the average sound pressure level at 5 points in the reverberation room.
Transmission power: Calculated from the acoustic intensity of 5 × 5 = 25 points in the inner 550 mm × 550 mm region of the sample opening surface.

Evaluation was made with reference to sound transmission loss (L (dB)) in Comparative Example 1 described later. Three samples were produced and evaluated based on their average value.
A: L + 0.2 dB or more;
○: L + 0.1 dB or more;
Δ: L-over 0.1 dB and less than L + 0.1 dB;
X: L-0.1 dB or less.

(Manufacture of samples for adhesion test)
A sample 40 shown in FIG. 5 was manufactured. FIG. 5 shows a top plan view of the sample 40 and a schematic sectional view thereof. In FIG. 5, the sample 40 was specifically manufactured by fixing the resin base material 41 to the steel plate 45 via the adhesive layer 42 using the spacer 46. Thereafter, the spacer was removed, and trimming was performed so that the bonded portion had a specified size. The dimensions of each member were as shown in FIG.

  The resin substrate 41 is a polycarbonate flat plate.

  The application shape (cross-sectional shape) of the adhesive layer 42 is 4 mm wide (b) × 5 mm high (h). The adhesive layer 42 was obtained by applying the urethane adhesive produced by the above-mentioned method with care so as not to entrap air bubbles and sufficiently solidifying the adhesive part with a 500 g weight while being bonded. is there.

  In manufacturing the sample 40, a black resin layer (not shown) was formed between the resin base material 41 and the adhesive layer 42. Specifically, a mixed polymer of polycarbonate and polyethylene terephthalate and carbon black were melted and mixed, applied to the resin base material 41, and cooled to form a black resin layer (thickness 3 mm). The surface roughness Ra of the surface of the black resin layer on which the adhesive layer 42 is formed was a value described in Table 1.

(Adhesion test)
Using the sample, the shear bond strength was measured. Specifically, it is measured by a method according to JIS K 6830: 1996 17.4 (test method) and displayed by a method according to 17.5 (display). However, the test speed is 200 ± 10 mm / min. Evaluation was based on the mode of destruction.
○: 100% of the fractured part was based on cohesive fracture in the adhesive layer;
Δ: Part of the fractured part was based on cohesive fracture in the adhesive layer;
X: 100% of the fractured part was based on the interface fracture between the adhesive layer and the black resin layer or the steel plate.

[Examples 2 to 8 and Comparative Examples 1 to 4]
By the same method as in Example 1 except that the surface roughness on the surface of the black resin layer forming the adhesive layer, the type of adhesive, and the application shape (cross-sectional shape) of the adhesive layer were changed as shown in Table 1. Samples were manufactured and evaluated.
As the adhesives B, C and D, the following adhesives were used.
The surface roughness Ra of the surface of the black resin layer on which the adhesive layer is formed in the sound insulation test sample 20 and the adhesion test sample 40 was adjusted to the values shown in Table 1.

(Manufacture of synthetic rubber adhesive: Adhesive B)
A synthetic rubber-based adhesive was produced by the following procedure using each component in the number of parts by weight shown below. First, after synthetic rubber was seated with a mixing roll, the synthetic rubber seated with a strong kneader was mixed and dissolved in a plasticizer. Next, after the remaining components were blended, the mixture was stirred and degassed for 60 minutes under a reduced pressure of 50 mmHg.
Synthetic rubber 1; 50 parts by weight of uncrosslinked synthetic rubber and butadiene rubber (Mooney viscosity 43);
Synthetic rubber 2; partially crosslinked synthetic rubber, SBR (Mooney viscosity 92, bound styrene content 23.5) 50 parts by weight;
-Crosslinking agent 1; 25 parts by weight of P-quinone dioxime;
-Plasticizer; 400 parts by weight of DINP (diisononyl phthalate);
-Foaming agent: 3.4 parts by weight of azodicarbonamide (average particle size 8 μm);
-Resin; 40 parts by weight of epoxy resin;
Curing agent: 5 parts by weight of dicyandiamide;
-Crosslinking accelerator 1; 5 parts by weight of zinc oxide;
-Cross-linking accelerator 2; 1 part by weight of stearic acid;
Filler: 400 parts by weight of heavy calcium carbonate (average particle size 8 μm).

  In the case of using a synthetic rubber adhesive, solidification for sample production was performed by heating the sample at 170 ° C. for 20 minutes.

(Manufacture of acrylic adhesive: Adhesive C)
An acrylic adhesive was produced by kneading the following components in parts by weight under reduced pressure.
"Dainar RB2000" manufactured by Mitsubishi Rayon Co., Ltd., A monomer: n-butyl methacrylate, mixed B monomer: methyl methacrylate / acrylic acid, particle size 30 μm; 112 parts by weight;
-100 parts by weight of calcium carbonate;
-90 parts by weight of surface treated calcium carbonate;
-150 parts by weight of diisononyl phthalate;
-10 parts by weight of a blocked urethane prepolymer;
-Fujicure FXE-1000; 1 part by weight of a polyamine-based modified compound (aliphatic polyamine derivative) manufactured by Fuji Kasei Kogyo Co., Ltd .;
-5 parts by weight of calcium oxide.

The blocked urethane prepolymer is synthesized by the following method.
Polymer polyol [Asahi Glass Co., Ltd. “EL-920”, polyoxyalkylene ether polyol having a molecular weight of 4900, f = 3 graft polymerized with a mixed monomer of acrylonitrile and styrene] 100 g, MDI 12.3 g and dibutyltin dilaurate 0 .008 g was reacted at 80 ° C. for 5 hours (NCO / OH = 2.2) to obtain a terminal NCO-containing urethane prepolymer, 4.9 g of methyl ethyl ketoxime was added thereto, and reacted at 50 ° C. for 5 hours. After confirming that NCO absorption has disappeared by IR, a blocked urethane prepolymer is obtained.

  In the case where an acrylic adhesive was used, solidification for sample production was performed by heating the sample at 140 ° C. for 20 minutes.

(Adhesive D)
As the adhesive D, a modified epoxy adhesive (manufactured by Sunstar Giken) was used.

The resin member of the present invention is useful as a vehicle member, an optical member, a building member, or the like.
Examples of the vehicle member include vehicle window members such as a roof window, a front window, a triangular window, a rear window, a rear quarter window, and a back window.

1:21:41: Resin base material 2: Colored resin layer 3:22:42: Adhesive layer 5: Other member (for example, vehicle body)
10: Resin member

Claims (9)

A resin member including a resin base material and an adhesive layer for fixing the resin base material to another member,
The width b (mm) and a height h (mm) and the storage modulus of the adhesive constituting the adhesive layer (Young's modulus) E (MPa) and loss factor tanδ of the adhesive layer meets the following relationship,
Resin member in which the adhesive layer is formed in an annular shape at a peripheral end portion on one surface of the resin base material :
0.03 ≦ tan δ × (h / Eb) The resin according to claim 1, further comprising an annular colored resin layer formed at a peripheral end portion on one surface of the resin base material, wherein the adhesive layer is formed annularly on the surface of the colored resin layer. Element. A resin member including a resin base material and an adhesive layer for fixing the resin base material to another member,
The width b (mm) and a height h (mm) and the storage modulus of the adhesive constituting the adhesive layer (Young's modulus) E (MPa) and loss factor tanδ of the adhesive layer meets the following relationship,
A resin member further comprising an annular colored resin layer formed at a peripheral end on one surface of the resin base material, wherein the adhesive layer is formed annularly on the surface of the colored resin layer :
0.03 ≦ tan δ × (h / Eb) H / Eb is 0.1 to 3.5,
The resin member according to any one of claims 1 to 3 , wherein the tan δ is 0.1 or more. The h / b is 0.5-3,
The resin member according to any one of claims 1 to 4 , wherein the tan δ / E is 0.01 to 2. When the thickness of the resin substrate is T1 (mm),
The width b is 0.5 × T1 to 2.5 × T1,
Wherein the height h is 0.5 × T1~2.0 × T1, the resin member according to any one of claims 1-5. The resin member is a vehicle, a resin member according to any one of claims 1-6. The resin member is a vehicle window member;
The resin substrate is a transparent resin substrate;
The resin member according to claim 7 , wherein the colored resin layer is a black resin layer. Vehicle body structure having a resin member according to claim 7 or 8.

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