JP2019172860A - Creaking sound prevention material - Google Patents

Abstract

To provide a creaking sound prevention material good in discharge property and shape retention property during un-curing, hardly being broken during engaging operation after curing, and excellent in adhesiveness.SOLUTION: A creaking sound prevention material contains an active energy ray curing resin composition (A) mainly containing silicone with E hardness of 30 to 45 at a curing state, and at least a silane coupling agent (B) having long chain aliphatic acid chain and a first silica fine particle with a particle diameter of 100 to 200 nm (C1) and a second silica fine particle with a particle diameter of 5 to 20 nm (C2), and has blended percentage of the first silica fine particle and the second silica fine particle of 10 to 80 pts.wt. and 0.5 to 10 pts.wt. respectively based on 100 pts.wt. of the active energy ray curing resin composition (A), viscosity at shear rate of 1 sat a state of un-curing of 50 to 1000 Pa s and E hardness (according to JIS K6253) at a cured state of 50 or more.SELECTED DRAWING: None

Description

  The present invention relates to a squeaking noise preventing material that prevents squeaking noise generated by vibration contact between adjacent components, and more particularly to a squeaking noise preventing material that is applied to a surface of a component that is in contact with vibration and cured.

  In a structure composed of a plurality of parts, there is a gap between adjacent parts, so that noise may be generated when the wall surfaces of adjacent parts rub or collide due to deformation or vibration of the structure. . Particularly in vehicles such as automobiles and trains, interior parts rub against each other due to vibration during running, and for example, squeaking noise is generated in the instrument panel, seat mold pad, door trim, etc. In order to make it have, it has been devised to prevent this itching sound. As one of the contrivances, a non-woven fabric is applied to the rubbing part to reduce squeaking noise, and a drug (smudge noise preventing agent) is applied.

  However, the method of applying non-woven fabric and applying medicine (anti-smacking agent) can prevent stagnation noise, but the method of applying non-woven fabric depends on the shape of the target part and the situation of assembly. In addition, the non-woven fabric to be affixed must be different in size (width and length), thickness, density, etc., and it is extremely difficult to manage. Further, this affixing operation is difficult to automate by a machine. For this reason, there was a problem in productivity because it was necessary to work manually. Further, in the method by applying a chemical such as wax, the periphery of the part surface to which the chemical is applied may be sticky, so that it cannot be applied to a part touched by a person, and the durability of the squeaking noise prevention performance is inferior.

  Therefore, as a technology that achieves both squeaking noise prevention performance and workability, an ultraviolet curable liquid active resin is discharged and applied to the surface of the component from the nozzle, and immediately after application, the liquid active resin is cured by irradiating the ultraviolet ray to the active coating film A method of forming a layer (Patent Document 1) has been proposed. In addition, in the same method of UV curing after application, it is possible to improve the squeaking noise prevention performance by blending 1 to 50% by weight of a spherical filler containing a UV curable resin as a main component and containing silicone spheres. Materials have been proposed. (Patent Document 2)

JP-A-3-143574 Patent Registration No. 2959682

  As in Patent Document 1 and Patent Document 2, an ultraviolet curable liquid squeaking noise prevention material is applied to the surface of a component by discharging from a nozzle, and immediately after application, a cured layer is formed that is cured by irradiating with ultraviolet rays to prevent squeaking noise. In this method, a process is performed in which a hardened layer is formed at a part where a stagnation sound is generated with the part removed, and the processed part is fitted into a predetermined position. In this fitting operation, while pressing the formed one hardened layer against the surface of one adjacent part, the other hardened layer is fitted in contact with the other part edge and the side of the adjacent part, so that a large shear is applied to the hardened layer. Force was applied, and the hardened layer was easily damaged and dropped off from the surface of the component, leaving room for improvement. Moreover, in order to form a hardened layer in a predetermined shape at a predetermined location, an uncured (liquid) stagnation sound preventing material is required to be easily applied by ejection and excellent in shape retention after coating. It was.

  Therefore, the present invention was made to solve the above-mentioned problems of the prior art, and its purpose is good dischargeability and shape retention at the time of uncured, and at the time of fitting work after curing. An object of the present invention is to provide a squeaking noise preventing material that is not easily damaged, has excellent adhesion to parts, and has excellent squeaking noise prevention properties. Another object is to provide a container filled with the uncured squeaking noise prevention material.

In order to solve the above-mentioned problems, the squeaking noise preventing material of the present invention is used by applying and curing to a part where adjacent parts interfere with each other, and an active energy ray-curable resin composition mainly composed of silicone. The product (A) comprises at least a silane coupling agent (B) and silica fine particles (C), and the E energy (according to JIS K6253) in the cured state of the active energy ray-curable resin composition (A) is 30 to 45. The silane coupling agent (B) has a long chain fatty acid chain, and the silica fine particles (C) have a particle diameter of 5 to 20 nm with the first silica fine particles (C1) having a particle diameter of 100 to 200 nm. Second silica fine particles (C2), and the blend ratio of the first silica fine particles (C1) and the second silica fine particles (C2) is the active energy ray-curable resin composition (A). 10 to 80 parts by weight and 0.5 to 10 parts by weight with respect to 100 parts by weight, respectively, in an uncured state, the viscosity at a shear rate of 1 s ⁻¹ is 50 to 1000 Pa · s, and in a cured state , E hardness (according to JIS K6253) is 50 or more.

As the active energy ray-curable resin composition (A) mainly composed of silicone, a cured product having sufficient strength can be obtained by setting the E hardness (conforming to JIS K6253) in a cured state to 30 to 45. it can. Moreover, sufficient adhesiveness with a base material can be obtained because a silane coupling agent (B) has a long-chain fatty acid chain. Further, the silica fine particles (C) comprise first silica fine particles (C1) having a particle size of 100 to 200 nm and second silica fine particles (C2) having a particle size of 5 to 20 nm, The blending ratio of the fine particles (C1) and the second silica fine particles (C2) is 10 to 80 parts by weight and 0.5 to 10 parts by weight, respectively, with respect to 100 parts by weight of the active energy ray-curable resin composition (A). By doing so, the surface slipperiness and the strength are compatible at the time of curing, so that it is difficult to break during the fitting operation, and it is easy to apply the coating when not cured, and a viscosity suitable for shape retention is obtained. Further, when the viscosity at a shear rate of 1 s ⁻¹ is 50 to 1000 Pa · s in an uncured state, a squeaking noise preventing material excellent in coating property and coating shape accuracy in an uncured state can be obtained. And the squeaking noise preventing material having each configuration of the present invention has an E hardness (conforming to JIS K6253) of 50 or more by irradiating and curing an active energy ray, and has sufficient strength and excellent adhesion. The provided cured product can be formed.

  It is also preferable that the silane coupling agent (B) of the squeaking noise preventing material of the present invention is an epoxy silane coupling agent. As a result, a squeaking noise preventing material having excellent adhesion when irradiated with active energy rays and cured is obtained.

  Moreover, it is also preferable that the epoxy-type silane coupling agent of the squeaking noise preventing material of the present invention is glycidoxyoctyltrimethoxysilane. As a result, a squeaking noise preventing material having even better adhesion can be obtained.

  Moreover, content of the silane coupling agent (B) of the squeaking sound prevention material of this invention is 0.5-10 with respect to 100 weight part of active energy ray-curable resin compositions (A) which have silicone as a main component. It is preferable that it is a weight part. Thereby, the squeaking noise preventing material having stable adhesion can be obtained.

  Furthermore, it is preferable that the carbon content of the first silica fine particles (C1) and the second silica fine particles (C2) of the silica fine particles (C) of the squeaking noise preventing material of the present invention is less than 0.5% by mass. Thereby, the applicability | paintability and shape accuracy are further excellent in the uncured state, and the squeaking sound preventing material having sufficient strength at the time of curing can be obtained.

  The container of the present invention is filled with any of the above-mentioned uncured squeaking noise prevention materials. The container is preferably light-shielding, and with this configuration, the stagnation sound prevention material can be stably stored in an uncured state. It can be applied stably.

The squeaking noise preventing material of the present invention is based on an active energy ray-curable resin composition (A) mainly composed of silicone having an E hardness (conforming to JIS K6253) of 30 to 45 in a cured state, and a long chain fatty acid chain. By including the silane coupling agent (B) having the above, the adhesion between the squeaking noise preventing material after curing and the component is improved, and the first silica fine particles (C1) having a particle size of 100 to 200 nm and the particle size are increased. 5 to 20 nm of second silica fine particles (C2) and 10 to 80 parts by weight and 0.5 to 10 parts by weight, respectively, with respect to 100 parts by weight of the active energy ray-curable resin composition (A), uncured in the state, the viscosity at a shear rate of ^{1s -1} is 50~1000Pa · s, and in the cured state, by E hardness (JIS K6253 compliant) is 50 or more, in the uncured state It is possible to achieve both good state retention and coating properties, and after curing, it has the strength to prevent breakage during fitting of parts, and exhibits excellent vibration proofing and buffering properties, so workability and quality reliability It is possible to prevent stagnation noise while improving

It is a schematic diagram which shows the application pattern of the bead discharge body for a test of the applicability | paintability at the time of non-hardening in an Example, and shape retention property. It is a schematic diagram explaining the method of the adhesive test in an Example and a comparative example.

  The squeaking noise preventing material of the present invention comprises at least a specific silane cup in an active energy ray curable resin composition (A) (hereinafter, simply referred to as an active energy ray curable resin composition (A)) containing silicone as a main component. It contains a ring agent (B) and specific silica fine particles (C).

  The active energy ray-curable resin composition (A) used for the squeaking noise preventing material of the present invention has a polymerizable functional group which is mainly composed of silicone and can be cured by active energy rays, and is E in a cured state. Hardness (based on JIS K6253) is 30-45. When the E hardness in the cured state is less than 30, sufficient strength as a squeaking noise preventing material cannot be obtained, and when the E hardness exceeds 45, the hardness after curing of the squeaking noise preventing material becomes too hard and sufficient stagnation The effect of preventing sound cannot be obtained.

The active energy ray-curable resin composition (A) has, for example, the following formula [1] (in the formula [1], R ¹ represents hydrogen or an alkyl group, R ⁿ represents (CH ₂ ) _n , 1 ≦ n ≦ 20.) Organopolysiloxane having at least one acrylic group or methacryloyl group represented by

Unsaturated double bond represented by the following formula [2] (in formula [2], R ¹ represents hydrogen or an alkyl group, R ⁿ represents (CH ₂ ) _n , and 0 ≦ n ≦ 10). An organopolysiloxane containing

Organopoly having at least two mercaptoalkyl groups represented by the following formula [3] (in formula [3], R ⁿ represents (CH ₂ ) _n , and 0 ≦ n ≦ 10)) Made by mixing siloxane.

  Here, the above-mentioned active energy rays refer to infrared rays, visible rays, ultraviolet rays, X-rays, electron rays, alpha rays, beta rays, or gamma rays, and ultraviolet rays are particularly preferably used. The ultraviolet rays in the present invention include near ultraviolet rays (near UV, wavelength 200 to 380 nm), far ultraviolet rays (wavelength 10 to 200 nm), and extreme ultraviolet rays (extreme UV, wavelength 1 to 10 nm). These active energy rays can be used alone or in combination of two or more. The source of these active energy rays is not particularly limited as long as it can be cured in a short time after coating or application of an uncured stagnation sound preventing material to the substrate to be coated. For example, a low pressure mercury lamp, a high pressure A known generation means such as a mercury lamp, an excimer ultraviolet (excimer UV) lamp, a halide lamp, an LED light, or a laser can be used. Examples of the infrared ray source include a lamp, a resistance heating plate, or a laser. Examples of the visible ray source include direct sunlight, a lamp, a fluorescent lamp, an LED light, and a laser. As an electron beam source, for example, a system using a thermoelectron generated from a commercially available tungsten filament, a cold cathode system that generates a metal through a high voltage pulse, and an ionized gaseous molecule and a metal electrode Examples include secondary electron type devices that utilize secondary electrons generated by collision. Furthermore, as a source of alpha rays, beta rays, and gamma rays, for example, a fission material such as Co60 can be cited. For gamma rays, a vacuum tube that collides accelerated electrons with the anode can be used. These active energy rays may be irradiated alone or in combination of two or more.

  The silane coupling agent (B) used for the squeaking noise preventing material of the present invention has a structure in which an organic functional group and Si having a silanol skeleton are interposed via a long-chain fatty acid chain. Due to the structure through the long fatty acid chain, the degree of freedom of the organic functional group is large and the reactivity is high, which contributes to improving the adhesion between the squeaking noise preventing material after curing and the part surface. The long chain fatty acid chain preferably has 8 or more carbon atoms, and if the carbon number is less than 7, the adhesion may be insufficient. As the terminal organic functional group, an epoxy group, an amino group, a vinyl group, an acrylic group or the like can be applied, and an epoxy group is particularly preferable from the viewpoint of adhesion. As the epoxy-based silane coupling agent having a long-chain fatty chain, known ones can be applied, but glycidoxyoctyltrimethoxysilane is particularly preferable from the viewpoint of adhesion. As glycidoxyoctyltrimethoxysilane, KBM-4803 manufactured by Shin-Etsu Silicone Co., Ltd. can be applied.

  The content of the silane coupling agent (B) is preferably 0.5 to 10 parts by weight, and 1 to 5 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin composition (A). Is more preferable. If the content of the silane coupling agent (B) is less than 0.5 parts by weight, sufficient adhesion may not be obtained. If it exceeds 10 parts by weight, the E hardness of the squeaking noise preventing material in the cured state is small. Since the strength may be insufficient, the above range is preferable.

  The silica fine particles (C) used for the squeaking noise preventing material of the present invention are composed of first silica fine particles (C1) having a particle size of 100 to 200 nm and second silica fine particles (C2) having a particle size of 5 to 20 nm. It contains. The first silica fine particles (C1) are components that improve the strength while maintaining the flexibility of the cured squeaking noise preventing material. The second silica fine particle (C2) is a component for adjusting the viscosity of the uncured stagnation sound preventing material and contributes to the coating property and the shape retention of the coated material.

  The first silica fine particles (C1) have a particle diameter of 100 to 200 nm. If the particle size of the first silica fine particles (C1) is out of the above range, sufficient strength may not be obtained. The mixing ratio of the first silica fine particles is 10 to 80 parts by weight, preferably 25 to 50 parts by weight, based on 100 parts by weight of the active energy ray-curable resin composition (A). When the blending ratio of the first silica fine particles is less than 10 parts by weight, the E hardness of the squeaking noise preventing material in the cured state becomes small and sufficient strength cannot be obtained, and when it exceeds 80 parts by weight, the E hardness increases. This is not preferable because a sufficient squeaking noise prevention effect cannot be obtained.

  The second silica fine particles (C2) have a particle diameter of 5 to 20 nm. If the particle size of the second silica fine particles (C2) is out of the above range, there may be a problem in coating properties. The blending ratio of the second silica fine particles (C2) is 0.5 to 10 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of the active energy ray-curable resin composition (A). . If the blending ratio of the second silica fine particles is less than 0.5 parts by weight, the viscosity is low and applicability becomes a problem, and if it is 10 parts by weight or more, the viscosity becomes too high to be discharged from the needle. Therefore, it is not preferable.

Here, the particle diameters of the first silica fine particles (C1) and the second silica fine particles (C2) are primary particle diameters, and in an image with a magnification at which the primary particles can be visually recognized with an SEM or a TEM (transmission electron microscope). This is a numerical value obtained by measuring the longest diameter of each of the primary particle images of 1000 randomly selected fine particles and arithmetically averaging them. The specific surface area (DIN 66131 compliant BET method) corresponding to the primary particle size is that the density of the silica fine particles is 2.0 g / cm ³ and the specific surface area of the first silica fine particles (C1) is 15 to 30 m ² / g. The specific surface area of the second silica fine particles (C2) is 15 to 600 m ² / g.

  As the first silica fine particles (C1) and the second silica fine particles (C2), known silica fine particles can be applied as long as they exhibit the above-mentioned particle size range and operational effects, but the above-mentioned operational effects are more easily obtained. Fumed silica is preferred. Of the fumed silica, hydrophilic silica fine particles not subjected to hydrophobic treatment are particularly preferable. By using hydrophilic silica fine particles, strength and surface slipperiness can be obtained while providing adhesion after curing. Here, fumed silica is a general term for aggregates obtained by treating a silane compound in a high-temperature atmosphere, and the obtained aggregates are compounds composed of silicon, oxygen and hydrogen in the same way as glass. In particular, it is called hydrophilic silica. In addition, fumed silica is industrially used in many fields, and a process called hydrophobization may be performed depending on its application and production method. The hydrophobic treatment is performed by treating hydrophilic silica with a compound having an organic functional group containing carbon, and therefore the hydrophobic silica fine particles contain a carbon component. Therefore, from the viewpoint of having hydrophilicity, the carbon content of the silica fine particles is preferably low. Specifically, the carbon content of the first silica fine particles (C1) and the second silica fine particles (C2) is the silica fine particles. It is less than 0.5 mass% with respect to the whole particle | grains, More preferably, it is 0.3 mass% or less, More preferably, it is 0.1 mass% or less, and it is especially preferable that a carbon component is not included. Specific examples of silica fine particles that can be used as the first silica fine particles (C1) and the second silica fine particles (C2) include AEROSIL (registered trademark) of Nippon Aerosil Co., Ltd., REOLOSIL (registered trademark) of Tokuyama Co., Ltd., and CABOT. CAB-O-SIL (registered trademark), fumed silica typified by WACKER HDK (registered trademark) manufactured by Asahi Kasei Wacker, NIPSIL (registered trademark) of Nippon Silica Kogyo Co., Ltd. TOKUSIL (registered trademark) of the company.

  If necessary, the squeaking noise preventing material of the present invention may be blended with other additives as long as the effects of the present invention are not impaired. Other additives include, for example, fillers, and include not only powder fillers but also conductive agents, static eliminating agents, flame retardants, buffering improvers, colorants, and the like. Examples of these powder fillers include crystalline silica, fused silica, calcium carbonate, talc, mica, alumina, aluminum hydroxide, and white carbon. Moreover, carbon black, expanded graphite powder, powdered graphite, metal fine particles, or the like can be used for imparting electrical conductivity or charge removal. As the flame retardant, a powdery organic halogen compound, red phosphorus, antimony trioxide, expanded graphite, magnetite, aluminum hydroxide, or the like can be used. As the buffering property improving agent, a hollow filler having an organic shell (for example, EXPANCEL (registered trademark) manufactured by Nippon Philite Co., Ltd.) can be used. Examples of the colorant include various pigments and dyes, and these additives may be appropriately selected and used depending on the application.

The squeaking noise preventing material of the present invention has a viscosity at a shear rate of 1 s ⁻¹ of 50 to 1000 Pa · s in an uncured state. If the viscosity is less than 50 Pa · s, it will flow too much after being ejected from the needle, etc., resulting in poor shape retention, and if it exceeds 1000 Pa · s, it will be difficult to eject from the needle, etc. This is not preferable because it tends to be cut easily and radial expansion is likely to occur. In addition, since the squeaking noise preventing material of the present invention exhibits the characteristics of a non-Newtonian fluid in an uncured state, the viscosity in the present invention is an apparent viscosity (hereinafter simply referred to as viscosity), and is based on JIS Z8803 (1991). It is a value measured under the condition of 25 ° C. according to “Viscosity Measurement Method Using Cone-Plate Rotational Viscometer”. Moreover, an uncured state is a state in which the active energy ray curable resin composition is not irradiated with an active energy ray for curing.

  The squeaking noise preventing material of the present invention is liquid in an uncured state and is cured by irradiation with active energy rays. The cured squeaking noise preventing material has an E hardness (based on JIS K6253) of 50 or more. If the E hardness is less than 50, it is not preferred because it easily breaks due to the shear stress at the time of component fitting. The upper limit of E hardness is not limited as long as it can prevent squeaking noise, but if E hardness becomes too high, it becomes difficult to absorb the vibration energy of the component. Therefore, it is preferably 80 or less as a guide. Therefore, by setting the E hardness in the range of 50 to 80, the squeaking noise preventing material exhibits a sufficient anti-vibration property while having sufficient strength.

  The squeaking noise preventing material of the present invention is produced by a known method for producing a resin composition. Specifically, as an example, an active energy ray-curable resin composition (A) and a silane coupling agent (B) using a kneader such as a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, or a roll mill. It is manufactured by adding silica fine particles (C) to a resin material kneaded and uniformly dispersing.

  The squeaking noise preventing material of the present invention is ejected in a bead shape or a dot shape from a needle-like coating portion by a pressurizing means to form a discharge body, and simultaneously or subsequently, the discharge body is irradiated with active energy rays and cured. Thus, it is possible to form a squeaking noise preventing material at a desired location. The squeaking noise preventing material of the present invention has a good vibration proofing property, and has sufficient strength, surface slipperiness, and adhesion to the component surface. Even when the preventive material is rubbed, it is possible to stably exhibit a squeaking noise preventing effect without causing damage to the squeaking noise preventing material or peeling from the surface of the component.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not particularly limited to these examples.

  The measurement methods of physical properties and the evaluation methods of effects in the following examples and comparative examples are as follows.

(1) Viscosity Viscosity at a shear rate of 1.0 s ⁻¹ at 25 ° C. using a corn-plate viscometer DT-3T manufactured by Brookfield according to JIS Z8803 (cone-plate rotational viscometer). Was measured.

(2) Hardness (E hardness)
An uncured squeaking noise prevention material is cast into a transparent resin mold having a diameter of 13 mm and a height of 6.3 mm, and cured by irradiating 365 nm ultraviolet rays from the top and bottom surfaces of ² J / cm ² each. A measurement sample was obtained. In the measurement, E hardness was measured using a type E durometer according to JIS K6253.

(3) Coating properties (dischargeability)
An air-pressurized dispensing device with an ultraviolet irradiation device attached to a container filled with an uncured stagnation sound prevention material in a light-shielding syringe equipped with a needle having an inner diameter φ1.1 mm and a circular discharge port cross-sectional shape ( It was mounted on a model Shotmaster (registered trademark) 200DS manufactured by Musashi Engineering Co., Ltd. While applying arbitrary air pressure in the container and discharging the uncured stagnation sound preventing material from the needle having an inner diameter of φ1.1 mm in a bead shape at 16 mm / s, while moving the needle at a speed of 15 mm / s, A bead-shaped discharge body having the pattern shown in FIG. 1 was formed. At this time, when the uncured stagnation sound preventing material can be discharged from the needle at 16 mm / s, the coating property is “◯” (pass: good), and the discharge is possible, but the needle moving speed (15 mm / s) In addition, a composition in which the discharge speed is slow and the bead-shaped discharge body is easy to extend has a coating property of “△” (pass: acceptable), and a composition in which the discharge speed is extremely low or difficult to discharge is “×” ( Failed).

(4) Shape retention property of bead-shaped discharge body in uncured state Container filled with uncured stagnation sound prevention material in light-shielding syringe with a circular cross-sectional shape of discharge port and a needle having an inner diameter of φ1.1 mm Was attached to an air pressure type dispensing device (model Shotmaster (registered trademark) 200DS manufactured by Musashi Engineering Co., Ltd.) to which an ultraviolet irradiation device was attached. A bead-like discharge body was formed on a glass plate (manufactured by Hiraoka Glass Co., Ltd., soda glass) with the same discharge speed of the uncured stagnation sound preventing material from the needle having an inner diameter of φ1.1 mm and the moving speed of the needle. . The bead-shaped discharge body was left to stand for 30 seconds, and the shape change (degree of sagging) of the bead-shaped discharge body was observed. When the width and height of the bead-shaped ejector are measured using a microscope (Nikon MM-800-LFA), and the ratio of the line height to the line width (height / width) is 0.7 to 1 Shape retention is “◯” (pass: good), shape retention is “△” (pass: acceptable) when less than 0.5 to 0.7, shape retention is “×” when less than 0.5 "(Fail).

(5) Adhesiveness A container filled with an uncured stagnation sound prevention material in a light-shielding syringe with a circular cross-sectional shape of the discharge outlet and a needle having an inner diameter of 1.9 mm is attached to an air heater with an ultraviolet irradiation device attached. It was attached to a pressure type dispensing device (Model Shot Master (registered trademark) 200DS manufactured by Musashi Engineering Co., Ltd.). A flat plate made of ABS resin of 100 mm × 200 mm × thickness 3 mm with the discharge speed of the uncured squeak noise prevention material from the needle having an inner diameter of 1.9 mm and the moving speed of the needle being the same (manufactured by UMG ABS Co., Ltd.) TM20) a 50 mm bead-shaped discharge body formed linearly, cured by irradiation with 365 nm ultraviolet rays at ² J / cm ^2, and a bead-shaped cured product having a height of about 2 mm was formed as an evaluation sample. did. As shown in FIG. 2 (a), the ABS resin flat plate 2 (100 mm × 200 mm × thickness 3 mm) is moved to a jig 4 that moves horizontally with respect to the ABS resin flat plate surface on which the evaluation sample is formed. TM20) manufactured by ABS Co., Ltd. is fixed to form a scraping spatula (scraper 3), which is placed on the linear bead-shaped cured product 111 as shown in FIG. 2 (b), and the scraper 3 as shown in FIG. 2 (c). Check the presence or absence of peeling of the cured product when it is moved 0.5 mm at a speed of 0.1 mm / s from the state in which the leading edge EL is in contact with the bead-shaped cured product 111 to the bead-shaped cured product. “○” indicates that no peeling was observed in the repeated test (pass: good), “△” indicates that the cured product was partially peeled (pass: acceptable), and the contact portion with the flat plate was completely peeled off “×” (failed) ).

(6) Strength (cured product)
The strength was evaluated from the E hardness of (2). An E hardness of 50 or more was judged as “◯” (pass: good), and an E hardness of less than 50 was judged as “x” (failed).

  The specifications of the silane coupling agent (B) used in the following examples and comparative examples are shown in Table 1, and the specifications of the first silica fine particles (C1) and the second silica fine particles (C2) are shown in Table 2. In Table 2, high plesica and AEROSIL are registered trademarks.

[Example 1]
Mercapto-modified silicone oil (KF2001 manufactured by Shin-Etsu Chemical Co., Ltd.) with 100 parts by weight of uncured active energy ray-curable silicone resin (Momentive TUV7110-CT: E hardness 20 when cured) in a plastic container with a lid ) Add 4.5 parts by weight and mix, 100 parts by weight of the active energy ray-curable resin composition (A) adjusted so that E hardness at the time of curing is 40, and as a silane coupling agent (B) 3 parts by weight of cidoxyoctyltrimethoxysilane (symbol b1 in Table 1), 35 parts by weight of fumed silica (spherical nanosilica FUME: symbol c12 in the table) having a particle size of 120 nm as the first silica fine particles (C1), Fumed silica having a particle size of 12 nm (AEROSIL200: in Table 1, symbol c2) as the second silica fine particles (C2) 2) 3 parts by weight of each are weighed in and sealed with a lid, and then set in a rotating / revolving mixer (product name: Awatori Rentaro (registered trademark) ARE-250, product of Sinky Corporation). The kneading sound preventing material was obtained by kneading for 3 minutes at 2000 rpm. Part of this squeaking noise prevention material is filled in a 50 mL light-shielding syringe and defoamed using a centrifugal defoamer for syringes (Product name: AWATRON (registered trademark) AW-50, product of Musashi Engineering Co., Ltd.). Then, a container filled with a squeaking noise preventing material was prepared and used as a sample for evaluating the coatability and the shape retaining property of the bead-shaped discharge body. On the other hand, the remaining squeaking noise preventing material that was not filled in the light-shielding syringe was used as a sample for measuring viscosity and hardness. Using these samples, the physical property measurement and evaluation of the squeaking sound preventing material obtained in Example 1 were performed.

[Example 2]
An active energy ray-curable silicone resin in an uncured state (TUV7110-CT manufactured by Momentive, Inc .: E hardness at curing: 20) 100 parts by weight of mercapto-modified silicone oil (KF2001 manufactured by Shin-Etsu Chemical Co., Ltd.) 2.3 parts by weight The active energy ray-curable resin composition (A) adjusted to have an E hardness of 30 upon curing was used, and the same method as in Example 1 except that the formulation shown in Table 3 was used. Thus, the squeaking noise preventing material of Example 2 and the container filled with it were obtained. In the same manner as in Example 1, physical property measurement and evaluation of each squeaking sound preventing material obtained in Example 2 were performed.

[Example 3]
5.7 parts by weight of mercapto-modified silicone oil (KF2001, Shin-Etsu Chemical Co., Ltd.) with respect to 100 parts by weight of uncured active energy ray-curable silicone resin (Momentive TUV7110-CT: E hardness at curing 20) The active energy ray-curable resin composition (A) adjusted to have an E hardness of 45 at the time of curing was used, and the same formulation as shown in Table 3 was used except that the formulation shown in Table 3 was used. By the method, the squeaking noise preventing material of Example 3 and a container filled with it were obtained. In the same manner as in Example 1, the physical properties of each squeaking sound preventing material obtained in Example 3 were measured and evaluated.

[Examples 4 to 6]
Using the active energy ray-curable resin composition (A) used in Examples 1 to 3, the silane coupling agent (B), the first silica fine particles (C1), and the second silica fine particles (C2) are obtained. A squeaking noise preventing material of Examples 4 to 6 and a container filled with it were obtained in the same manner as in Example 1 except that the composition shown in Table 3 was used. In the same manner as in Example 1, the physical properties of the squeaking noise preventing materials obtained in Examples 4 to 6 were measured and evaluated.

[Example 7]
3.4 parts by weight of mercapto-modified silicone oil (KF2001 manufactured by Shin-Etsu Chemical Co., Ltd.) with respect to 100 parts by weight of uncured active energy ray-curable silicone resin (TUV7110-CT manufactured by Momentive, which has an E hardness of 20 when cured) The active energy ray-curable resin composition (A) adjusted to have an E hardness of 35 at the time of curing was used, and the same formulation as shown in Table 3 was used except that the formulation shown in Table 3 was used. By the method, a squeaking noise preventing material of Example 7 and a container filled with it were obtained. In the same manner as in Example 1, physical property measurement and evaluation of each squeaking sound preventing material obtained in Example 7 were performed.

[Examples 8 to 11]
Except for the components shown in Table 4, the squeaking noise preventing materials of Examples 8 to 11 and a container filled with the same were obtained in the same manner as in Example 1. In the same manner as in Example 1, physical property measurement and evaluation of each squeaking sound preventing material obtained in Examples 8 to 11 were performed.

[Examples 12 to 13]
Example 1 except that octenyltrimethoxysilane (symbol b2) and methacryloxyoctyltrimethoxysilane (symbol b3) in Table 1 were used as the silane coupling agent (B), respectively, and the formulation shown in Table 4 was used. By the same method, the squeaking noise preventing material of Examples 12 and 13 and the container filled with it were obtained. In the same manner as in Example 1, the physical properties of the squeaking noise preventing materials obtained in Examples 12 and 13 were measured and evaluated.

[Examples 14 to 17]
Except for mainly changing the particle diameter and / or the composition of the first silica fine particles (C1) to make the respective components shown in Table 5, the same procedures as in Example 1 were followed. A squeaking noise prevention material and a container filled with it were obtained. In the same manner as in Example 1, the physical properties of each squeaking sound preventing material obtained in Examples 14 to 17 were measured and evaluated. In addition, the active energy ray-curable resin composition (A) used in Example 15 is the same as that used in Example 2.

[Examples 18 to 20]
It is the stagnation of Examples 18 to 20 in the same manner as in Example 1 except that the particle diameter and / or the composition of the second silica fine particles (C2) are mainly changed and the respective components are blended as shown in Table 5. A soundproofing material and a container filled with it were obtained. In the same manner as in Example 1, the physical properties of each squeaking sound preventing material obtained in Examples 18 to 20 were measured and evaluated.

  Tables 3, 4 and 5 show the physical property measurements and evaluation results of the squeaking noise preventing materials of Examples 1 to 7, Examples 8 to 13, and Examples 14 to 20, respectively.

[Comparative Example 1]
A squeaking sound preventing material of Comparative Example 1 having a viscosity in an uncured state of 30 Pa · S and a container filled with the same, except that the respective components are blended as shown in Table 6 in the same manner as in Example 1. Obtained. Similarly to Example 1, the physical properties of each squeaking sound preventing material obtained in Comparative Example 1 were measured and evaluated.

[Comparative Example 2]
A squeaking sound preventing material of Comparative Example 2 having a viscosity in an uncured state of 2000 Pa · S and a container filled with the same, except that each component is blended as shown in Table 6 in the same manner as in Example 1. Obtained. Similarly to Example 1, the physical properties of each squeaking sound preventing material obtained in Comparative Example 2 were measured and evaluated.

[Comparative Example 3]
Except for using the active energy ray-curable silicone resin (TUV7110-CT, manufactured by Momentive) having an E hardness of 20 as the active energy ray-curable resin composition (A), the formulation shown in Table 6 was used. In the same manner as in Example 1, the squeaking noise preventing material of Comparative Example 3 and a container filled with it were obtained. In the same manner as in Example 1, the physical properties of each squeaking sound preventing material obtained in Comparative Example 3 were measured and evaluated.

[Comparative Example 4]
As silane coupling agent (B), glycidoxypropyltrimethoxysilane (symbol b4) having no long-chain fatty acid chain shown in Table 1 was used, and the composition shown in Table 6 was used. By the method, the squeaking noise preventing material of Comparative Example 4 and a container filled with it were obtained. In the same manner as in Example 1, the physical properties of each squeaking sound preventing material obtained in Comparative Example 4 were measured and evaluated.

  Table 6 shows the physical properties and evaluation results of the squeaking noise preventing materials of Comparative Examples 1 to 4.

  From the evaluation results of Examples 1 to 20 shown in Tables 3 to 5, the squeaking noise preventing material of the present invention is excellent in uncured coating properties and shape retention, and the cured product has an E hardness of 50 or more. It was found that the material has excellent strength and adhesion to the substrate. The configuration of the present invention and the operation and effect thereof will be described with reference to the examples and comparative examples.

From the comparison of the evaluation results of Examples 1 to 20 and Comparative Examples 1 and 2, in the uncured state, if the viscosity at the shear rate of 1 s ⁻¹ of the squeaking noise preventing material is out of the range of 50 to 1000 Pa · s, itching It has been found that it is necessary to be within the scope of the present invention because the coating property of the sound-preventing material and the shape retaining property of the bead-like discharge body are lowered.

  Further, from the comparison of the evaluation results of Examples 1 to 20 and Comparative Example 3, in the cured state, when the E hardness is less than 50, the strength decreases, so the E hardness needs to be 50 or more. I understood it.

  From comparison of the evaluation results of Examples 1 to 20 and Comparative Example 4, it was found that excellent adhesion was obtained by using the silane coupling agent (B) having a long-chain fatty acid chain. Moreover, it turned out that it is preferable that a silane coupling agent (B) is an epoxy-type silane coupling agent from an adhesive viewpoint from the comparison of the evaluation result of Example 5 and Examples 12-13.

  From the evaluation results of Examples 8 to 11, the blending ratio of the silane coupling agent (B) is 0.5 parts by weight or more with respect to 100 parts by weight of the active energy ray-curable resin composition (A) from the viewpoint of adhesion. It turned out that it is more preferable. Moreover, although not described in the evaluation column of Tables 3 to 6, when the surface tackiness of the cured squeaking noise preventing material was observed with the finger, Example 11 was compared with the squeaking noise preventing material of Example 10. Since the squeaking noise preventing material obtained in (1) was sticky on the surface, it was found that when the silane coupling agent (B) exceeds a certain ratio, tackiness increases on the cured surface. From this result, considering the viewpoint of suppressing the surface tackiness, the blending ratio of the silane coupling agent is 0.5 to 10 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin composition (A). It turned out to be more preferable.

  The stagnation sound preventing material of the present invention is excellent in strength and has excellent adhesion to the base material, so that it is possible to prevent squeaking noise without causing damage or peeling of the squeaking sound preventing material when fitting parts. Therefore, it can contribute to the improvement of quality, and is useful as a material for preventing squeaking of a structure composed of a plurality of parts such as an automobile.

10 Bead discharger (uncured product)
11, 111 Itching prevention material (cured material)
2 Flat plate 3 Scraper
4 Jig

Claims (6)

The active energy ray-curable resin composition (A) mainly composed of silicone contains at least a silane coupling agent (B) and silica fine particles (C), and is applied to a portion where adjacent parts interfere with each other. It is a stagnation sound preventing material used by curing, and the E energy (based on JIS K6253) in the cured state of the active energy ray-curable resin composition (A) is 30 to 45, and the silane coupling agent (B) Has a long chain fatty acid chain, and the silica fine particles (C) are first silica fine particles (C1) having a particle size of 100 to 200 nm and second silica fine particles (C2) having a particle size of 5 to 20 nm. The mixing ratio of the first silica fine particles (C1) and the second silica fine particles (C2) is 100 parts by weight of the active energy ray-curable resin composition (A). 10 to 80 parts by weight and 0.5 to 10 parts by weight, respectively, in an uncured state, the viscosity at a shear rate of 1 s ⁻¹ is 50 to 1000 Pa · s, and in the cured state, E hardness (JIS K6253 (Compliance) is 50 or more.   The stagnation sound preventing material according to claim 1, wherein the silane coupling agent (B) is an epoxy silane coupling agent.   The squeaking noise preventing material according to claim 2, wherein the epoxy-based silane coupling agent is glycidoxyoctyltrimethoxysilane.   The content of the silane coupling agent (B) is 0.5 to 10 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin composition (A). The squeaking noise preventing material according to any one of the above items.   The carbon content of the first silica fine particles (C1) and the second silica fine particles (C2) is less than 0.5% by mass, according to any one of claims 1 to 4. Anti-smacking material. A container filled with the uncured stagnation sound preventing material according to any one of claims 1 to 5.