CN113550824A - Automobile waterproof box, light-cured organic silicon composition and organic silica gel - Google Patents
Automobile waterproof box, light-cured organic silicon composition and organic silica gel Download PDFInfo
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- CN113550824A CN113550824A CN202110441570.4A CN202110441570A CN113550824A CN 113550824 A CN113550824 A CN 113550824A CN 202110441570 A CN202110441570 A CN 202110441570A CN 113550824 A CN113550824 A CN 113550824A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 5
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- VSJBBIJIXZVVLQ-UHFFFAOYSA-N tert-butyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(C)(C)C VSJBBIJIXZVVLQ-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B77/00—Component parts, details or accessories, not otherwise provided for
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B77/00—Component parts, details or accessories, not otherwise provided for
- F02B77/11—Thermal or acoustic insulation
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Acoustics & Sound (AREA)
- Sealing Material Composition (AREA)
- Gasket Seals (AREA)
- Casings For Electric Apparatus (AREA)
Abstract
The invention provides a waterproof box for an automobile, which can reduce the cost required by assembly operation, can be reassembled, and has excellent heat resistance and waterproof performance, and a photo-curing type organic silicon composition or organic silicon gel used for the waterproof box. The waterproof box for an automobile comprises: the case body includes a housing space for housing an object to be housed, an opening communicating with the housing space, and a lid portion attached to the case body and closing the opening. Is sandwiched between the main body part and the lid partHas a structure selected from SO group, SO2Radical and SO3A sealing material comprising a silicone rubber having adhesion and containing at least 1 SOx group out of the groups. At least one of the main body and the lid is provided with a receiving portion, and an engaging projection that engages with the receiving portion is provided at a position corresponding to the receiving portion of the main body and the lid.
Description
Technical Field
The present invention relates to a waterproof case for an automobile, a photocurable silicone composition, and a silicone rubber.
Background
An engine room of an automobile is provided with electrical components such as an ECU (i.e., an electronic control unit) for an engine, a flow path switching valve, an electronic throttle valve, a battery pack, a power control unit, a camera for recognizing white lines and the like, and a LiDAR (i.e., light detection and ranging) sensor. These electric components include objects to be stored such as electronic components, sensors, and gears, and a case for storing the objects to be stored. The cartridge has: a box main body part which is provided with a containing space for containing the objects and an opening communicated with the containing space; and a sealing material interposed between the case body and the lid portion to liquid-tightly seal therebetween.
Conventionally, a rubber gasket such as an O-ring or a gasket has been used as a sealing material. For example, patent document 1 describes the following technique: a sealing material made of heatable butyl rubber was applied to the sealing surface of at least one of the 2 casing parts.
In recent years, there are also techniques of: a so-called liquid gasket, which is formed by applying a liquid curable composition to a desired portion and curing the composition at the desired portion to form a gasket, is used as a sealing material.
In addition, there are techniques as follows: the liquid-tight seal between the box main body and the lid is performed by bonding the box main body and the lid with an adhesive.
Documents of the prior art
Patent document
Patent document 1: japanese Kohyo publication No. 2001-525985
Disclosure of Invention
When a rubber gasket or a liquid gasket as described in patent document 1 is used as the sealing material, it is necessary to fasten the lid portion to the case main body portion via a fastening member such as a bolt and sufficiently compress the gasket interposed therebetween in order to liquid-tightly seal the case main body portion and the lid portion. Therefore, the component cost of the fastening member itself and the work cost required for the fastening work are generated, which hinders the cost reduction of the electric components.
Further, when an O-ring or a gasket is used as the sealing material, it is necessary to arrange these components by manual work. Therefore, in this case, the cost of the electrical components may be further increased.
On the other hand, when the box main body and the lid portion are bonded together using an adhesive, the lid portion and the box main body do not need to be fastened together, and a fastening member for fastening the lid portion and the box main body does not need to be used. However, in this case, after the lid portion is bonded to the box main body portion, when it is necessary to remove the lid portion from the box main body portion for some reason, the cured adhesive has to be broken. In order to avoid the above problem, a sealing material is desired which can be attached to the case main body once and then can be reassembled by removing the cover from the case main body.
Further, since the engine generating high heat is disposed in the engine room, the temperature in the engine room varies widely from the outside air temperature to the high temperature during engine operation. Therefore, such a sealing material is required to have high heat resistance in addition to waterproof performance.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a waterproof case for an automobile, which can be reassembled with reduced costs required for assembly work and has excellent heat resistance and waterproof performance, and a photocurable silicone composition and a silicone gel that can be used for the waterproof case for an automobile.
One embodiment of the present invention is a waterproof box (1, 102) for an automobile, comprising:
a box main body part (2) provided with a storage space (21) for storing objects to be stored and an opening (22) connected with the inside of the storage space;
a lid portion (3, 302) attached to the case main body portion and closing the opening;
a sealing material (4) consisting of a material having a structure selected from the group consisting of SO groups and SO groups2Radical and SO3At least 1 SOx group of the groups and a tacky silicone rubber interposed between the case main body and the lid;
a receiving part (31) provided on at least one of the case main body part and the lid part; and
and an engaging projection (23) provided at a position corresponding to the receiving portion in the case main body portion and the lid portion, and engaged with the receiving portion.
Another embodiment of the present invention is a photocurable silicone composition comprising the following components (A) to (D) SO as to be capable of forming a silicone composition having an SO group or an SO group2Radical and SO3At least 1 SOx-based silicone gum among the groups:
(A) the components: a polyorganosiloxane having a vinylsiloxane group,
(B) the components: a mercapto-based crosslinking agent, a crosslinking agent,
(C) the components: a radical-based photoinitiator, which is a radical-based photoinitiator,
(D) the components: an organic peroxide having a 10-hour half-life temperature of 150 ℃ or less.
Another embodiment of the present invention is a silicone rubber obtained by curing the photocurable silicone composition of the above embodiment, the silicone rubber having a structure selected from the group consisting of SO groups and SO groups2Radical and SO3At least 1 SOx group of the radicals.
The waterproof box for an automobile (hereinafter, abbreviated as "waterproof box") includes: the box body part is provided with a containing space and a cover part mounted on the box body part. In addition, at least one of the main body portion and the lid portion is provided with a receiving portion. In addition, the engaging convex portion is provided at a position corresponding to the receiving portion in the case main body portion and the lid portion, and the engaging convex portion is engaged with the receiving portion. That is, the box body portion and the lid portion are locked by so-called snap-fit.
The waterproof box can be attached to the box body portion by a simple operation of pressing the engaging convex portion into the receiving portion. In the waterproof box, the cover portion may be attached to the box main body portion without using a fastening member such as a bolt. Therefore, according to the waterproof box, the part cost of the fastening member can be reduced, and the work cost required for the attachment work of the lid portion and the box main body portion can be reduced.
Further, a sealing material made of the aforementioned SOx-based and adhesive silicone rubber is interposed between the case main body portion and the lid portion. The organic silicone rubber having the SOx group can be bonded to the lid portion and the case main body portion when the lid portion is attached to the case main body portion, and can close the gap between the sealing material and the lid portion and the gap between the sealing material and the case main body portion. This makes it possible to seal the lid portion and the case body portion in a liquid-tight manner. Further, since silicone rubber has high heat resistance, it can maintain water-repellent performance for a long period of time even in an engine room.
In the waterproof box, the lid portion can be easily removed from the box main body portion after the lid portion is once attached to the box main body portion by engaging the box main body portion and the lid portion with a snap fit and by using the specific silicone rubber as a sealing material. After the lid portion is removed from the box main body portion, the lid portion is attached to the box main body portion again, whereby the lid portion and the box main body portion can be liquid-tightly sealed with each other by the sealing material.
The photocurable silicone composition may contain the components (A) to (D) and may be formed to have a structure selected from the group consisting of SO group and SO group2Radical and SO3At least 1 of the groups is an SOx group silicone rubber. Therefore, according to the photocurable silicone composition, the silicone gel having the SOx group can be formed. Further, since the SOx-based silicone rubber has excellent adhesion to the case body and the lid, when used as a sealing material for a waterproof case, it can maintain waterproof performance for a long period of time.
As described above, according to the above-described aspect, it is possible to provide a waterproof case which can be reassembled with reduced costs required for assembly work and is excellent in heat resistance and waterproof performance, and a photocurable silicone composition or silicone rubber which can be used for the waterproof case.
The parenthesized reference signs described in the claims and the means for solving the problems indicate the correspondence with the specific means described in the embodiments described later, and do not limit the technical scope of the present invention.
Drawings
Fig. 1 is a sectional view showing a main part of a waterproof box according to embodiment 1.
Fig. 2 is a partially enlarged view of the sealing material in fig. 1.
Fig. 3 is a partially enlarged sectional view showing a main part of the waterproof case in embodiment 2 in which the projection is press-fitted with the sealing material.
Fig. 4 is an explanatory diagram showing the tensile shear bond strengths of the test pieces II to KK in experimental example 2.
Fig. 5 is an explanatory diagram showing X-ray absorption spectra of test piece LL and test piece MM in experimental example 3.
Fig. 6 is an explanatory diagram showing X-ray absorption spectra of the test piece NN and the test piece OO in experimental example 4.
Description of the symbols
1. 102 waterproof box
2 case body part
21 accommodating space
22 opening
23 engaging projection
3. 302 cover part
31 receiving part
4 sealing Material
Detailed Description
(embodiment mode 1)
An embodiment of the waterproof box will be described with reference to fig. 1 to 2. The waterproof case of the present embodiment is a case to be attached to an automobile, and specifically, a waterproof case to be attached to an automobile to accommodate an object to be accommodated. As shown in fig. 1, the waterproof box 1 of the present embodiment includes: a box main body 2 having a storage space 21 for storing the stored articles and an opening 22 connected to the storage space 21, and a cover attached to the box main body 2 for sealing the opening 22A closed cover part 3. A cover part 3 and a case body part 2 having a structure selected from the group consisting of SO group and SO group2Radical and SO3A sealing material 4 made of a silicone rubber having at least 1 SOx group among the groups and having adhesiveness. In addition, a receiving portion 31 is provided in at least one of the case main body portion 2 and the lid portion 3, and an engaging convex portion 23 that is engaged with the receiving portion 31 is provided in a position corresponding to the receiving portion 31 in the case main body portion 2 and the lid portion 3.
The shape and structure of the waterproof box 1 are not particularly limited. For example, the waterproof box 1 may have a 1-position housing space 21 surrounded by the box main body portion 2 and the cover portion 3, or may have a 2-position or more housing space 21. The number of the openings 22 connected to the housing space 21 may be 1 or 2.
Although not shown in the drawings, the waterproof case 1 of the present embodiment has a rectangular parallelepiped shape. As shown in fig. 1, the main body 2 includes a bottom wall 24, a side wall 25 standing from an outer peripheral edge of the bottom wall 24, and an accommodation space 21 surrounded by the bottom wall 24 and the side wall 25. Further, the waterproof case 1 has an opening 22 surrounded by the front end 251 of the side wall portion 25.
As shown in fig. 2, the cartridge main body 2 of the present embodiment has a sealing material holding groove 26 having a bottom surface 261 and a side surface 262 continuous with the bottom surface 261 at a front end 251 of the side wall portion 25. The sealing material holding groove 26 is provided around the entire periphery of the front end 251 of the side wall portion 25. The sealing material 4 is disposed on the bottom surface 261 of the sealing material holding groove 26.
As shown in fig. 1, a plurality of engaging protrusions (also simply referred to as protrusions) 23 protruding outward are provided on the outer surface of the side wall portion 25. These engaging projections 23 are inserted into receiving holes 311 of receiving section 31 described later. Thereby, the engaging convex portion 23 is locked to the receiving portion 31. That is, the engaging projection 23 is physically fixed to the receiving portion 31 by being inserted into the receiving hole 311 of the receiving portion 31 and biting with the receiving portion 31.
The case main body portion 2 of the present embodiment is configured to be able to accommodate an object to be accommodated in the accommodating space 21. The object to be stored in the storage space 21 includes, for example, components of an automobile, more specifically, electronic devices such as an electronic circuit, a sensor, and a motor, and driving components such as gears.
The opening 22 of the box main body portion 2 is covered with the lid portion 3. The lid 3 of the present embodiment is flat, and as shown in fig. 2, has a sealing surface 32 in contact with the sealing material 4 at its outer periphery. Further, a plurality of receiving portions 31 extending and protruding toward the case main body portion 2 side are provided on the edge of the lid portion 3. Although not shown in the drawings, the receiving portion 31 of the present embodiment has a ring shape. As shown in fig. 2, the receiving portion 31 is provided with a receiving hole 311 for receiving the engaging projection 23. The engaging projection 23 is inserted into the receiving hole 311.
The case main body 2 and the lid 3 may be formed of a metal such as iron or aluminum, a resin such as an engineering plastic or a super engineering plastic, or a metal and a resin, for example. From the viewpoint of reducing the weight of the waterproof case 1, at least one of the case main body portion 2 and the lid portion 3 is preferably formed of a resin, and more preferably both are formed of a resin. The case main body 2 and the lid 3 of the present embodiment are both made of polyamide resin.
In the present embodiment, the space between the case body 2 and the lid 3 is liquid-tightly sealed by using silicone rubber having adhesiveness as the sealing material 4. Silicone rubber is extremely soft compared to a rubber gasket such as an O-ring, and therefore can reduce the pressure applied to the sealing material 4 compared to a conventional waterproof case in which sealing is performed using a rubber gasket. Therefore, even when a resin having a lower rigidity than metal is used for the case main body portion 2 and the lid portion 3, the sealing material 4 can be sufficiently compressed, and the waterproof performance can be ensured.
As shown in fig. 1 and 2, a sealing material 4 made of an SOx-based adhesive silicone rubber is interposed between the case main body portion 2 and the lid portion 3. As shown in fig. 2, the sealing material 4 is disposed on the bottom surface 261 of the sealing material holding groove 26. As shown by a broken line in fig. 2, the sealing member 4 has a mountain-like cross-sectional shape in a state (denoted by reference numeral 40) where the cover portion 3 is not attached, and a central portion in the width direction protrudes further than the front end 251 of the side wall portion 25. In a state where the lid portion 3 is attached to the main body portion 2, the lid portion 3 is compressed by the sealing surface 32 of the lid portion 3 as shown by a solid line in fig. 2.
Here, the silicone gel means a gel of a polymer containing polysiloxane. The silicone rubber is preferably one obtained by curing a composition containing a curable organopolysiloxane compound. In the following, in order to distinguish between before and after curing, a composition in a state before curing, that is, a composition in a liquid state at 25 ℃ is referred to as a silicone composition, and a gel-like composition after curing is referred to as a silicone gel.
The viscosity of the silicone composition at 25 ℃ is not particularly limited, and is preferably 200 to 600 pas. In this case, the discharge property of the silicone composition can be further improved, and the flow of the silicone composition after coating can be suppressed, so that the shape of the silicone composition after discharge can be easily maintained for a longer period of time. The silicone composition preferably has a structural viscosity ratio of 2.5 to 5.5 at 25 ℃. In this case, the flow of the silicone composition after coating can be suppressed, the shape of the silicone composition after discharge can be easily maintained for a longer period of time, and corner portions are less likely to be formed in the silicone composition after coating.
The silicone composition is formed into a silicone gel by reacting an organopolysiloxane compound having a functional group with the action of heat, moisture, light, or the like to form a polymer. The silicone gel has adhesiveness, that is, a property of performing adhesion only by pressing the silicone gel.
As the silicone composition, for example, a heat-curable silicone composition, a moisture-curable silicone composition, and a photo-curable silicone composition can be used. The silicone composition is particularly preferably a photocurable silicone composition.
Examples of the heat-curable silicone composition include, but are not limited to, a composition containing a polyorganosiloxane having a vinyl siloxane group and a peroxide, a polyorganosiloxane having a vinyl siloxane group, a composition containing a hydrogen siloxane compound and a hydrosilylation metal catalyst, and a composition containing a polyorganosiloxane having an epoxy group and a thermal cationic catalyst. These may be used alone, or 2 or more of them may be used in combination.
Examples of the moisture-curable silicone composition include, but are not limited to, polyorganosiloxanes having hydrolyzable silyl groups, compositions containing silane-based coupling agents and condensation catalysts, polyorganosiloxanes having isocyanate groups, and compositions containing polyol compounds and condensation catalysts. These may be used alone, or 2 or more of them may be used in combination.
Examples of the photocurable silicone composition include, but are not limited to, a composition containing a polyorganosiloxane having a (meth) acrylic group and a radical photoinitiator, a polyorganosiloxane having a vinylsiloxane group, a composition containing a polythiol compound and a radical photoinitiator, and a composition containing a polyorganosiloxane having an epoxy group and a photocationic catalyst. These may be used alone, or 2 or more of them may be used in combination.
The heat-curable silicone composition, the moisture-curable silicone composition, and the photocurable silicone composition may be composed of a single component or may be composed of two or more components. From the viewpoint of forming the sealing material 4 in situ, it is preferable to use a photocurable silicone composition that can be cured at a low temperature for a short time by a device such as an ultraviolet irradiator or an LED irradiator.
The organic silica gel contains SO group or SO group2Radical and SO31 or 2 or more kinds of SOx groups among the groups. These SOx groups are usually bonded to the polysiloxane chain in the silicone rubber. By using the specific silicone rubber, it is possible to effectively suppress the entry of moisture or the like from between the case main body portion 2 and the lid portion 3, and to improve the waterproof performance. The specific silicone gel may have the following reasons for the above-described effects. Since the SOx group has high polarity, for example, when the cartridge main body portion 2 and the lid portion 3 have polar groups such as a hydroxyl group, an amide group, and a carboxyl group, hydrogen bonding to these polar groups is possible. It is presumed that the adhesion between the silicone rubber and the case main body portion 2 and the adhesion between the silicone rubber and the lid portion 3 can be improved by hydrogen bonding of the SOx group and the polar group.
The SOx groups in the silicone gel may be formed by various methods. For example, the SOx group can be formed by curing a composition containing a curable organopolysiloxane compound and a mercapto crosslinking agent having an SH group, and then oxidizing the SH group and the thioether group in the obtained silicone gel. The method for oxidizing the SH group or the sulfide group is not particularly limited, and for example, the SH group or the sulfide group can be oxidized by contacting the silicone gel with an oxidizing atmosphere. Alternatively, the composition may be formed by adding an oxidizing agent capable of oxidizing an SH group or a thioether group to the composition before curing, and reacting the oxidizing agent with the SH group or thioether group during or after curing of the composition. Further, the composition or silicone gel being cured can be heated to promote oxidation of SH groups or sulfide groups. Alternatively, the silicone composition may contain SOx groups in advance.
The hardness of the silicone rubber can be determined by JIS K6253-3: 2012 is expressed in durometer hardness obtained by a type E durometer. The hardness of the sealing material 4 when the E-hardness meter is pressed with a load of 1kg is not particularly limited, and is preferably 5 to 30, for example. At this time, when the lid portion 3 is attached to the case main body portion 2 and the sealing member 4 is compressed, the repulsive force of the sealing member 4 can be increased as appropriate. As a result, the waterproof performance of the waterproof box 1 can be further improved.
The tensile shear adhesion strength of the sealing material 4 is not particularly limited, and is, for example, preferably 0.10MPa or more, more preferably 0.20MPa or more, and still more preferably 0.25MPa or more. In this case, when the lid portion 3 is attached to the box main body portion 2 and the sealing material 4 is compressed, the adhesion force of the sealing material 4 to the lid portion 3 and the adhesion force of the sealing material 4 to the box main body portion 2 can be increased, and the waterproof performance of the waterproof box 1 can be further improved.
From the viewpoint of further improving the water-repellent performance of the waterproof case 1, it is preferable to use, as the sealing material 4, a silicone rubber obtained by curing a photocurable silicone composition containing the following components (a) to (C), and more preferably a silicone rubber obtained by curing a photocurable silicone composition containing the components (a) to (D).
(A) The components: polyorganosiloxanes having vinylsiloxane groups
(B) The components: mercapto group-based crosslinking agent
(C) The components: radical photoinitiator
(D) The components: oxidizing agents capable of oxidizing SH groups and thioether groups
The photocurable silicone composition containing the components (a) to (D) is configured such that the polymerization reaction of the polyorganosiloxane is induced by irradiation with energy rays such as visible light rays and ultraviolet rays. In addition, by previously adding the oxidizing agent (component (D)) to the photocurable silicone composition, SH groups and thioether groups present in the cured silicone gel can be reacted with the oxidizing agent, and the SH groups and thioether groups in the silicone gel can be easily oxidized. Therefore, according to the photocurable silicone composition, the silicone gel having the SOx group can be formed.
The molecular structure of the polyorganosiloxane having a vinylsiloxane group (component (a)) is preferably linear, and may have a branched structure. Examples of the polyorganosiloxane include dimethylvinylsiloxy-terminated dimethylsiloxane at the molecular chain end, dimethylvinylsiloxy-terminated dimethylsiloxane/diphenylsiloxane copolymer at the molecular chain end, dimethylvinylsiloxy-terminated dimethylsiloxane/methylvinylsiloxane/diphenylsiloxane copolymer at the molecular chain end, dimethylsiloxane having one molecular chain end blocked with dimethylvinylsiloxy groups and the other molecular chain end blocked with trimethylsiloxy groups, methylvinylsiloxane/diphenylsiloxane, trimethylsiloxy-terminated dimethylsiloxane/methylvinylsiloxane copolymer at both molecular chain ends, And dimethylsiloxy-terminated dimethylsiloxane-methylvinylsiloxane-diphenylsiloxane copolymers at both molecular chain terminals, but the invention is not limited thereto. These may be used alone, or 2 or more of them may be used in combination. The functional group equivalent (i.e., the equivalent of vinyl group) of the aforementioned polyorganosiloxane with a vinylsiloxane group is not particularly limited, and is preferably 100g/eq to 50000g/eq, for example.
As the mercapto group-based crosslinking agent (component (B)), for example, a polythiol compound having a plurality of SH groups in one molecule can be used. Examples of the polythiol compound include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoglycolate), butanediol bis (3-mercaptoglycolate), trimethylolpropane tris (3-mercaptoglycolate), pentaerythritol tetrakis (3-mercaptoglycolate), tris- [ (3-mercaptopropionyloxy) -ethyl ] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane, and mixtures thereof, Polyorganosiloxane having a mercapto group, polysulfide polymer having a mercapto group, and the like, but are not limited thereto. These may be used alone, or 2 or more of them may be used in combination. By using a cured product of a silicone composition containing a mercapto crosslinking agent as the sealing material 4, the adhesion of the sealing material 4 to the lid portion 3 and the adhesion of the sealing material 4 to the case main body portion 2 can be increased, and the waterproof performance of the waterproof case 1 can be further improved. The mercapto crosslinking agent is preferably a polythiol compound having 2 or more mercapto groups (thio-) in 1 molecule.
The photocurable silicone composition may contain 1 compound selected from the group consisting of the compounds having a mercapto group as the component (B), or may contain 2 or more compounds. The equivalent of the functional group (i.e., the equivalent of the mercapto group) of the component (B) is preferably 100 to 50000 g/eq.
The content of the component (B) in the photocurable silicone composition is not particularly limited, and is preferably 0.1 to 10 parts by mass, for example, per 100 parts by mass of the component (a). The photocurability can be further improved by setting the content of the component (B) to 0.1 part by mass or more. Further, by setting the content of the component (B) to 10 parts by mass or less, the storage stability can be further improved. The content of the component (B) is more preferably 0.50 to 5.0 parts by mass with respect to 100 parts by mass of the component (a) from the viewpoint of further increasing the adhesive force of the sealing material 4 to the lid portion 3 and the adhesive force of the sealing material 4 to the case main body portion 2.
The radical photoinitiator (component (C)) is not particularly limited as long as it is a compound capable of promoting the reaction between the vinylsiloxane group and the mercapto group by irradiation with light. Examples of the radical photoinitiator include 1-hydroxy-cyclohexylphenylketone, 2-dimethoxy-2-acetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4 ' -dimethoxybenzophenone, 4 ' -diaminobenzophenone, michelson, benzoin propyl ether, benzoin ethyl ether, benzil dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [ 4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2-dimethoxy-2-acetophenone, 4 ' -diaminobenzophenone, MII-methyl ketone, MII-methyl-2-methyl-1-one, 2-morpholinopropan-1-one, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, and the like, Bis- (2, 6-dimethoxybenzoyl) -2, 4, 4-trimethylpentylphosphine oxide, and the like, but is not limited thereto. The radical photoinitiator may be used alone or in combination of 2 or more. The radical photoinitiator is preferably a compound having an absorption peak wavelength in the ultraviolet region and/or visible light region.
The content of the component (C) in the photocurable silicone composition is not particularly limited, and is preferably 0.1 to 5.0 parts by mass, for example, per 100 parts by mass of the component (a). The photocurable property can be obtained by setting the content of the component (C) to 0.1 parts by mass or more. Further, the storage stability can be further improved by setting the content of the component (C) to 5.0 parts by mass or less.
As the oxidizing agent (component (D)) contained in the photocurable silicone composition, a compound capable of oxidizing an SH group and a sulfide group can be used. More specifically, a peroxide, preferably an organic peroxide, can be used as the oxidizing agent. The 10-hour half-life temperature of the organic peroxide as the oxidizing agent is not particularly limited, and is, for example, preferably 150 ℃ or lower, and more preferably 60 to 110 ℃. The half-life is an index indicating the decomposition rate of the organic peroxide at a certain temperature, and means the time required until the active oxygen amount becomes 1/2 as the original organic peroxide is decomposed. The 10-hour half-life temperature is a temperature at which the half-life of the organic peroxide is 10 hours when the organic peroxide is decomposed at a certain temperature.
The organic peroxide as the component (D) is preferably a peroxyester, and more preferably has a molecular structure represented by the following general formula (1) or the following general formula (2).
R1－O－O－CO－R2General formula (1)
R3－O－O－CO－O－R4General formula (2)
(R5－CO－O－O)n－R6General formula (3)
R in the general formula (1), the general formula (2) and the general formula (3)1～R6Each independently a substituted or unsubstituted aromatic group, a hydrocarbon group selected from aliphatic hydrocarbon groups and unsaturated hydrocarbon groups. N is a natural number of 1 or more.
Examples of the aromatic group include a monocyclic aromatic group such as a substituted or unsubstituted phenyl group, a condensed polycyclic aromatic group such as a substituted or unsubstituted naphthyl group, and an unfused polycyclic aromatic group such as a biphenyl group. The aromatic group may have 1 or 2 or more substituents, and examples of the substituents include aliphatic hydrocarbon groups described later. The aromatic group may be bonded to the adjacent oxygen atom in the formulae (1), (2), and (3) through a substituent. The number of carbon atoms in the aromatic group is not particularly limited, and is, for example, 6 to 40, preferably 6 to 20.
Examples of the aliphatic hydrocarbon group include a straight-chain alkyl group, a branched-chain alkyl group, and a cyclic alkyl group. Examples of the straight-chain alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl groups. Examples of the branched alkyl group include isopropyl group, tert-butyl group, and isobutyl group. Examples of the cycloalkyl group include cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. It is noted that the cycloalkyl group may be substituted with a straight chain alkyl group and/or a branched chain alkyl group. The number of carbon atoms in the aliphatic hydrocarbon group is not particularly limited, and is, for example, 1 to 40, preferably 1 to 20, and more preferably 1 to 10.
Examples of the unsaturated hydrocarbon group include a vinyl group, an n-propenyl group, an n-butenyl group, an n-pentenyl group, an n-hexenyl group, an n-heptenyl group, an n-octenyl group, an n-nonenyl group, an n-decenyl group, an n-undecenyl group, and an n-dodecenyl group. The number of carbon atoms in the unsaturated hydrocarbon group is not particularly limited, and is, for example, 1 to 40, preferably 1 to 20, and more preferably 1 to 10.
The above-mentioned hydrocarbon group may be bonded to adjacent oxygen atoms in the formulae (1), (2), and (3) at an arbitrary site. When the hydrocarbon group is polyvalent, adjacent oxygen atoms in the formulae (1), (2) and (3) may be bonded instead of an arbitrary hydrogen atom in the hydrocarbon group.
Examples of the organic peroxide that can be used as the component (D) in commercially available organic peroxides include the following products. PERHEXYL PV, PERBUTYL PV, PERHEXYL 25O, PERROCAT O, PERHEXYL O, PERBUTYL L, PERBUTYL 355, PERHEXYL I, PERBUTYL E, PERHEXYA 25Z, PERHEXYL Z, PERBUTYL Z, PERCUTYL ND, PERCHITA ND, PERHEXYL ND, PERBUTYL A, PERBURE O, etc., manufactured by Nissan oil Co. These organic peroxides may be used alone, or 2 or more of them may be used in combination. The component (D) is not limited to the above-mentioned products. The "PERHEXYL", "perrutyl", "perrexa", "percta" and "PERCUMYL" are registered trademarks of japan oil co.
The content of the component (D) in the photocurable silicone composition is not particularly limited, and is preferably 0.1 to 5.0 parts by mass, for example, per 100 parts by mass of the component (a). When the content of the component (D) is 0.1 parts by mass or more, the SOx group can be more reliably formed in the silicone rubber obtained by curing the photocurable silicone composition. This can further improve the adhesion between the sealing material 4 and the case body 2 and the adhesion between the sealing material 4 and the lid 3. Further, by setting the content of the component (D) to 5.0 parts by mass or less, the storage stability can be further improved.
The silicone composition may further contain a filler as the component (E). Examples of the filler include, but are not limited to, inorganic fillers such as calcium carbonate powder, silica powder, fumed silica powder, talc powder, aluminum hydroxide powder, and glass beads, and organic fillers such as polystyrene powder, polyurethane powder, acrylic acid powder, silicone rubber powder, and silicone resin powder. The specific surface area of the filler measured by the BET method is not particularly limited from the viewpoint of controlling the flowability of the composition, and is preferably 105m, for example2/g～135m2(ii) in terms of/g. From the same viewpoint, the particle size of the filler is not particularly limited, and is preferably, for example, 1nm to 100 μm. When the particle size of the filler is in the nm range, the particle size of the filler is a value calculated based on an electron microscopic image. In the case where the particle size of the filler is in the order of μm, the particle size of the filler is a value based on a 50% average particle size (so-called d50) of a particle size distribution obtained by using a laser particle sizer. The filler is preferably composed of silica.
In the silicone composition, a pigment, a colorant, a plasticizer, a flame retardant, an antioxidant, a polymerization inhibitor, a defoaming agent, a coupling agent, a leveling agent, a rheology control agent, and the like may be further added within a range not impairing the characteristics thereof. By adding these other components, a composition excellent in resin strength, adhesive strength, workability, storage stability and the like, and a cured product thereof can be obtained.
The photocurable silicone composition is preferably configured to be curable by irradiation with energy rays such as ultraviolet rays and visible light. In this case, energy consumption in the manufacturing process of the waterproof box 1 can be further reduced, and running cost in the manufacturing can be further reduced. As the irradiation device for irradiating the energy ray, for example, a SPOT type irradiation device having an energy ray source configured to be capable of locally irradiating the energy ray to the object to be processed and configured to be movable, a conveyor type irradiation device having an energy ray source configured to be capable of irradiating the energy ray and a conveyor configured to move the object to be processed with respect to the energy ray source, and the like can be used. In addition, as the energy source, for example, an LED (i.e., light emitting diode) lamp, a high-pressure mercury lamp, or the like can be used. From the viewpoint of further reducing energy consumption in the manufacturing process, it is preferable to use an LED lamp with low power consumption as the energy source.
The sealing member 4 of the present embodiment is disposed on the bottom surface 261 of the sealing member holding groove 26, and is compressed by the bottom surface 261 and the sealing surface 32 of the lid portion 3. Further, a gap is formed between the side surface 262 of the seal material holding groove 26 and the seal material 4. By disposing the sealing member 4 in this manner, a gap for deforming the sealing member 4 can be ensured when the lid portion 3 is attached to the case main body portion 2. This can avoid an excessive increase in the repulsive force of the sealing material 4 when the sealing material 4 is compressed. As a result, it is possible to avoid an excessive increase in the load applied to the receiving portion 31 and the engaging convex portion 23, and to maintain the state in which the engaging convex portion 23 is engaged with the receiving portion 31 for a longer period of time.
In the present embodiment, the sealing material 4 is compressed so that the height Hf compressed between the case main body 2 and the lid 3 is 40 to 80% of the height Hi in the uncompressed state. By setting the compression amount of the sealing material 4 within the above-described specific range, the repulsive force of the sealing material 4 can be increased appropriately when the lid portion 3 is attached to the case main body portion 2 and the sealing material 4 is compressed. As a result, the waterproof performance of the waterproof box 1 can be further improved.
The waterproof box 1 of the present embodiment can be produced, for example, by a production method including the steps of: a coating step of coating a silicone composition on a desired portion of the case main body and the lid; a curing step of curing the silicone composition to form the sealing material; and a mounting step of mounting the lid portion to the case main body portion with the sealing material interposed therebetween and engaging the engaging protrusion with the receiving portion.
In the coating step, for example, the following method can be employed: the silicone composition is discharged from the coating nozzle while the coating nozzle is moved along the portion where the sealing material is to be disposed, using a coating apparatus provided with the coating nozzle configured to discharge the silicone composition.
In the curing step, an appropriate curing method corresponding to the curing system of the silicone composition may be used. For example, when the silicone composition is a heat-curable silicone composition, the silicone composition can be cured to form a sealing material by heating the silicone composition after the application of the silicone composition to the case main body portion and/or the lid portion is completed.
When the silicone composition is a photocurable silicone composition, the coating step and the curing step may be performed as separate steps, or may be performed continuously. In the former case, for example, the following method can be employed: after the application of the photocurable silicone composition is completed in the application step, the entire photocurable silicone composition is irradiated with an energy ray to form the sealing material 4.
In the latter case, the following method may be employed: in the coating step, the photocurable silicone composition applied to the desired portion is locally irradiated with the energy ray while the photocurable silicone composition is applied to the desired portion. In this case, since the coating step and the curing step can be performed in parallel, the number of steps can be reduced, and the productivity can be further improved. In this case, since the energy ray source can be downsized, the energy required for manufacturing the waterproof box 1 can be further reduced while the facility cost and the like can be further reduced.
More specifically, the above method can be carried out, for example, by using a coating apparatus having a coating nozzle configured to be capable of coating a photocurable silicone composition and an energy ray source configured to be capable of irradiating an energy ray, and moving the coating nozzle and the energy ray source so that the energy ray source follows the discharge nozzle.
Next, the operation and effects of the waterproof box 1 of the present embodiment will be described. The box body 2 and the lid 3 in the waterproof box 1 of the present embodiment are locked by so-called snap-fitting in which the engaging protrusion 23 is locked to the receiving portion 31. Therefore, the lid portion 3 can be attached to the box main body portion 2 by a simple operation of pressing the engaging convex portion 23 into the receiving portion 31. This can reduce the cost required for the assembly work of the waterproof box 1.
The space between the main body portion 2 and the lid portion 3 is sealed by a sealing material 4 made of silicone rubber having an SOx group and having adhesiveness. This makes it possible to seal the lid portion 3 and the case main body portion 2 in a liquid-tight manner, and to maintain the waterproof performance for a long period of time.
The waterproof box 1 can be easily detached from the box main body 2 after the cover 3 is once attached to the box main body 2 by engaging the box main body 2 and the cover 3 with a snap fit and using the silicone rubber having the above-described specific SOx group as the sealing material 4. Further, by removing the lid portion 3 from the case main body portion 2 and then attaching the lid portion 3 to the case main body portion 2 again, the space between the two can be sealed liquid-tightly with the sealing material 4.
As described above, according to the waterproof box 1 of the present embodiment, it is possible to provide the waterproof box 1 which can reduce the cost required for the assembly work, can be reassembled, and is excellent in heat resistance and waterproof performance. The waterproof case 1 of the present embodiment can be used, for example, by being disposed in an engine room of an automobile.
(embodiment mode 2)
As shown in fig. 3, the waterproof case 102 of the present embodiment has a protrusion 33 that protrudes from the outer peripheral portion of the cover 302 and is press-fitted into the sealing member 4. In the symbols used in embodiment 2 and thereafter, the same symbols as those used in the above-described embodiment indicate the same components and the like as those used in the above-described embodiment unless otherwise specified.
The waterproof box 102 of the present embodiment includes a box main body portion 2, a lid portion 302, and a sealing material 4 interposed between the box main body portion 2 and the lid portion 302. A projection 33 projecting toward the bottom surface 261 of the seal material holding groove 26 is provided at a position facing the seal material holding groove 26 in the case main body portion 2 and the lid portion 302, and the projection 33 is preferably press-fitted into the seal material 4. The protrusion 33 may be disposed at a position facing the sealing material holding groove 26. For example, the sealing material holding groove 26 of the present embodiment is disposed at the front end 251 of the side wall portion 25 in the cartridge main body portion 2. Therefore, the protrusion 33 of the present embodiment is provided at a position facing the sealing material holding groove 26, that is, the sealing surface 32, in the cover portion 302.
When the projection 33 is press-fitted into the sealing member 4 as in the present embodiment, the height of the portion compressed by the projection 33 is the height Hf of the sealing member 4 in a state compressed between the case main body portion 2 and the lid portion 302. That is, in the present embodiment, the distance from the bottom surface 261 of the seal material holding groove 26 to the projection 33 is the height Hf of the seal material 4 in a compressed state. The same as embodiment 1.
By providing the projection 33 as in the present embodiment, the compression amount of the sealing material 4 can be made larger than in the case where the projection 33 is not provided, and the repulsive force of the sealing material 4 can be made appropriately larger. Further, by press-fitting the projection 33 into the sealing member 4, the contact area between the projection 33 and the sealing member 4 can be increased, and the formation of a gap between the projection 33 and the sealing member 4 can be suppressed more effectively. As a result, the waterproof performance of the waterproof box 102 can be further improved. The waterproof box 102 of the present embodiment can provide the same operational effects as those of embodiment 1.
[ examples ]
(Experimental example 1)
This example is an example of evaluating the adhesion of silicone gels obtained by curing various silicone compositions. In this example, first, photocurable silicone compositions (compositions a to H) having the compositions shown in table 1 were prepared.
Specific examples of the compounds shown in table 1 are as follows.
(A) Composition (I)
Compound a: polydimethylsiloxane having vinylsiloxane group at the end (viscosity at 25 ℃ C.: 30000 mm)2/sFunctional group equivalent: 26000g/eq)
(B) Composition (I)
Compound B: polythiol Compound (viscosity at 25 ℃ C.: 200 mm)2Per s, functional group equivalent: 1900g/eq)
(C) Composition (I)
Compound C: radical photoinitiator (absorption peak wavelength: 244nm and 330nm)
(D) Composition (I)
Compound D1: organic peroxide (PERBUTYL I, manufactured by NOF corporation, 10-hour half-life temperature: 98.7 ℃ C.)
Compound D2: organic peroxide (PERCURE O, manufactured by NOF corporation, 10-hour half-life temperature: 72.1 ℃ C.)
Compound D3: organic peroxide (PERBUTYL I, manufactured by NOF corporation, 10-hour half-life temperature: 104.3 ℃ C.)
(D') component
Compound D' 1: organic peroxide (PERCUMYL H-80 manufactured by NOF corporation, 10-hour half-life temperature: 157.9 ℃ C.)
Compound D' 2: oleic acid (reagent)
Compound D' 3: heptanoic acid (reagent)
The component (D') is a comparative component with respect to the component (D).
(E) Composition (I)
Filler E: silica powder (specific surface area: 120 m) by sparse aqueous vapor phase method2(iv)/g, particle diameter: 20nm)
Specifically, the compositions A to H were prepared as follows. First, components (a) to (D) shown in table 1 and other components were weighed so as to be mass ratios shown in table 1, and charged into a stirred tank. Subsequently, the components (a) to (D) and other components in the stirred tank were mixed for 30 minutes and vacuum-defoamed. After the mixing and the vacuum defoaming were completed, the component (E) was weighed so as to have a mass ratio shown in table 1. After the weighed amount of component (E) was charged into a stirred tank, components (a) to (E) and other components in the stirred tank were mixed for 60 minutes and vacuum defoamed. Thus, compositions a to H were obtained.
[ Table 1]
The viscosity, the structural viscosity ratio and the adhesive force were measured by the following methods using the obtained compositions a to H.
[ measurement of viscosity and structural viscosity ratio ]
For the measurement of the viscosity and the structural viscosity ratio, a cone-and-plate type rotational viscometer (E-type viscometer) was used, the temperature of which was adjusted to 25 ℃ by means of a circulation thermostatic bath. 0.5cc of the compositions A to H was collected and discharged into the center of the sample cup. The sample cup was attached to the main body of the viscometer, and compositions a to H were sandwiched between a 3 ° × R12 cone plate and the sample cup. The conical plate was rotated at a rotational speed of 1.0rpm for 5 minutes in this state. The viscosity at the time when 5 minutes elapsed from the start of rotation was defined as the viscosity of compositions a to H and is shown in the column "viscosity" in table 2.
The viscosities of compositions a to H were measured in the same manner as in the above method except that the rotation speed of the conical plate was changed to 0.5rpm or 2.5 rpm. The values obtained by dividing the viscosity of the composition at the rotation speed of 0.5rpm by the viscosity of the composition at the rotation speed of 2.5rpm are shown in the column of "structural viscosity ratio" in table 2 as the structural viscosity ratios of the compositions a to H.
[ measurement of adhesive force ]
In order to evaluate the adhesive strength of silicone gels obtained by curing compositions a to H, the adhesive strength was measured in accordance with JIS K6850: 1999 tensile shear bond strength was measured. The test pieces AA to HH (see table 2) used for the measurement of the tensile shear adhesion strength were prepared in the following manner. First, 2 sheets of a covering material made of PA66 (i.e., nylon 66) and having dimensions of 80mm in length, 25mm in width, and 4mm in thickness were prepared. One of the 2 sheets of the coating material was overlaid with 2 sheets of spacers having a thickness of 1.5mm and attached thereto, thereby forming a 10mm × 15mm coated region surrounded by the spacers. Injecting composition A to E into the coating areaH, rolling was performed to make the composition smooth and flat, and the coating thickness of the compositions A to H was 3 mm. Thereafter, the composition is irradiated with ultraviolet rays using an ultraviolet irradiator equipped with an LED lamp to cure the composition, thereby forming a silicone gel on the coating material. The center wavelength of the ultraviolet light emitted from the LED lamp was 365 nm. The cumulative amount of ultraviolet light irradiated to the composition was 1500mJ/cm2。
After 1 separator was peeled from the coating material on which the silicone rubber was formed, the other coating material was bonded to the silicone rubber. Next, 2 sheets of the coating material were fixed and compressed with a clip to set the thickness of the silicone rubber to 50% of the initial thickness. The thus obtained test pieces AA to HH (see table 2) were held at a temperature of 100 ℃ for 300 hours in a hot air drying oven, and then the test pieces AA to HH were taken out from the hot air drying oven. And (4) cooling the test piece to room temperature, and then taking down the clamp.
The heated test pieces AA to HH were used, and the heat treatment was carried out in accordance with JIS K6850: 1999 tensile tests were performed. The crosshead speed of the tensile tester was 5 mm/min. The column "tensile shear bond strength" in table 2 shows the maximum strength in the tensile test. The state of the fracture surface was evaluated by visually observing the silicone rubber after the tensile test. In the column of "fracture state" in table 2, the symbol "a" is described when the entire adhesive surface is cohesive fracture, and the symbol "B" is described when the adhesive surface includes cross-sectional fracture.
[ Table 2]
As shown in table 2, the silicone gels obtained by curing compositions a to D had higher tensile shear bonding strength than the silicone gels obtained by curing compositions E to H. While the silicone rubbers obtained by curing the compositions a to D were all cohesively fractured at the bonding surface, the silicone rubbers obtained by curing the compositions E to H were partially fractured at the bonding surface. From these results, it is understood that when the photocurable silicone composition is cured using ultraviolet rays having low energy using an LED lamp as a light source, the adhesion of the silicone rubber can be improved by the photocurable silicone composition containing the component (D) compared to the photocurable silicone composition not containing the component (D).
Although not shown in the table, when the holding time at 100 ℃ was set to 24 hours, the tensile shear adhesion strength of the silicone rubber obtained by curing composition A was 0.28 MPa. From the results, it can be understood that the tensile shear bond strength can be increased by making the heating time longer.
Further, after storing the composition a and the composition D at 25 ℃ for 1 month, the viscosity of the composition a became 473Pa · s and the viscosity of the composition D became 549Pa · s. From a comparison of these viscosity values with the initial viscosity values shown in table 1, it was found that the compositions a and D had a small change in viscosity during storage and had sufficient storage stability.
(Experimental example 2)
In this example, the adhesion of the silicone rubber was evaluated when the coating material was PBT (i.e., polybutylene terephthalate). The method for producing the test piece in this example is as follows.
< test piece II >
The method for producing the test piece II was the same as the method for producing the test piece AA in experimental example 1, except that the material of the coating material was changed to PBT.
< test piece JJ >
The method for producing test piece JJ was the same as the method for producing test piece II except that composition E was used in place of composition a as the photocurable silicone composition and composition E was cured using an ultraviolet irradiator equipped with a high-pressure mercury lamp. The cumulative light amount of ultraviolet light irradiated by the high-pressure mercury lamp in the method for producing the test piece JJ was 4500mJ/cm2。
< test piece KK >
The method for producing test piece KK was the same as the method for producing test piece EE in experimental example 1, except that the material of the coating material was changed to PBT.
Tensile tests were carried out using the test pieces II to KK obtained above under the same conditions as in example 1, and the tensile shear adhesion strength of each test piece was measured.
The tensile shear adhesion strength of test pieces II to KK is shown in fig. 4. The vertical axis in fig. 4 represents tensile shear adhesion strength (MPa). In test pieces II and JJ, the entire adhesive surface was broken by the tensile test in the interior of the silicone rubber. On the other hand, in the test piece KK, a part of the adhesive surface was broken in a cross section between the silicone rubber and the covering material by a tensile test.
As shown in fig. 4, the tensile shear bonding strength of the silicone rubber in test piece II and test piece JJ is shown as a value higher than that of the silicone rubber in test piece KK. In addition, test piece II in which oxidation of SH groups and sulfide groups in the silicone rubber was promoted by the oxidizing agent exhibited higher tensile shear adhesion strength than test piece KK.
(Experimental example 3)
This example is an example of detailed investigation of the chemical state of the S atom in the silicone gel by X-ray absorption fine structure analysis using radiated light. In this example, first, a test piece LL simulating the test piece AA in experimental example 1 and a test piece MM simulating the test piece AA before heating were prepared. The specific manufacturing method of test piece LL and test piece MM is as follows.
< test piece LL >
Composition a was coated on a substrate made of PBT. The coating thickness of composition A was 10 μm. Next, the composition a coated on the substrate was irradiated with ultraviolet rays using an LED lamp as a light source under the same conditions as the test piece AA, and thereby the composition a was cured to prepare a silicone rubber. The cured silicone gel was heated together with the substrate at a temperature of 100 ℃ for 300 hours. The silicone gel is then separated from the substrate. The silicone gel obtained as described above, that is, the silicone gel obtained by heating the cured product of composition a was used as test piece LL.
< test piece MM >
The test piece MM was produced in the same manner as the test piece LL except that the silicone gel was prepared by curing the composition a and then heating the silicone gel was not performed.
The chemical states of the S atoms in the silicone gel in the test piece LL and the test piece MM obtained above were analyzed by a hard X-ray XAFS (X-ray absorption edge fine structure method). Specifically, the test piece LL and the test piece MM are irradiated with X-rays obtained by splitting the radiation beam, and absorption spectra near the X-ray absorption edge of the S atom are obtained. Then, based on the obtained absorption spectrum, the X-ray absorption fine structure of the S atom in the silicone gel was analyzed. Fig. 5 shows X-ray absorption spectra of test piece LL and test piece MM. The vertical axis of fig. 5 represents normalized absorption intensity, and the horizontal axis represents energy (eV) of incident light.
FIG. 5 shows an S atom derived from an SH group, an S atom derived from an SO group, and an SO group2S atom of radical and from SO3Position of absorption peak of S atom of radical. These peak positions are determined based on the absorption spectrum in the vicinity of the X-ray absorption edge of the reference sample having each functional group.
Note that the X-ray absorption spectrum was obtained in "known as SR Beamline BL6N1 in the known synchrotron optical center". The detection method is a fluorescence yield method, and the K terminal of the S atom is measured. Further, the beam diameter of the incident X-ray was 2.00mm × 1.00 mm.
As shown in fig. 5, in the X-ray absorption spectra of test piece LL and test piece MM, an absorption peak having a peak appears near 2475eV, and an absorption peak having a peak appears near 2481 eV. In addition, the absorption peak having a peak near 2481eV has a shoulder near 2479 eV. From these results, it can be understood that the silicone gels obtained by curing the photocurable silicone compositions containing the components (A) to (D) have SH groups and SO groups, as in the test pieces AA to DD and the test pieces LL to MM2Radical and SO3And (4) a base.
(Experimental example 4)
This example is an example in which the chemical states of the S atoms in the silicone gel in the test piece JJ and the test piece KK of experimental example 2 were examined in detail by X-ray absorption fine structure analysis using radiated light. In this example, first, a test piece NN simulating the test piece JJ and a test piece OO simulating the test piece KK in experimental example 2 were prepared. The specific methods of producing test piece NN and test piece OO are as follows.
< test piece NN >
The composition E was coated on a substrate made of PBT. The coating thickness of composition E was 10 μm. Next, the composition E applied to the substrate was irradiated with ultraviolet rays using a high-pressure mercury lamp as a light source under the same conditions as in the test piece JJ, and thereby the composition E was cured to prepare a silicone rubber. The silicone gel was held together with the substrate at a temperature of 100 ℃ for 300 hours in the atmosphere. Thus, a test piece NN simulating the test piece JJ was obtained.
< test piece OO >
The test piece OO was produced in the same manner as the test piece NN except that an LED lamp was used as a light source of ultraviolet light instead of the high-pressure mercury lamp.
The chemical states of the S atoms in the organic silica gel in the test piece NN and the test piece OO obtained above were analyzed by a hard X-ray XAFS (X-ray absorption edge fine structure method). The method and conditions for obtaining the X-ray absorption spectrum in this example were the same as those in experimental example 3, except that the silicone gel on the substrate was irradiated with X-rays.
Fig. 6 shows X-ray absorption spectra of S atoms in the test piece NN and the test piece OO. The vertical axis of fig. 6 shows normalized absorption intensity, and the horizontal axis shows energy (eV) of incident light. FIG. 6 shows an S atom derived from an SH group, an S atom derived from an SO group, and an SO group2S atom of radical and from SO3Position of absorption peak of S atom of radical. These peak positions are determined based on the absorption spectrum in the vicinity of the X-ray absorption edge of the reference sample having each functional group.
As shown in fig. 6, the X-ray absorption spectrum of the test piece NN showed an absorption peak having a peak near 2475eV, and a large absorption peak having a peak near 2481 eV. In addition, the larger peak having a peak near 2481eV has a shoulder near 2479 eV. From the X-ray absorption spectrum shown in FIG. 6, it can be understood that the silicone gel of the test piece NN, that is, the composition E, was cured by a high-pressure mercury lampThe heated organic silica gel has SH groups and SO groups2Radical and SO3And (4) a base.
In addition, the absorption peak of the S atom derived from the SH group in the test piece NN was shifted to the high energy side of about 200meV from the absorption peak of the reference sample. Furthermore, from SO3The absorption peak of the S atom of the radical is shifted to a lower energy side of about 200meV than that of the reference sample. It is inferred that the shift of these absorption peaks is due to SH groups and SO groups in the silicone gel in the test piece NN3The radical is caused by hydrogen bonding with the polar group of the coating material. Therefore, it is considered that the test piece JJ passes through SO in the organic silica gel3The base group is hydrogen-bonded to a polar group or the like of the coating material to exhibit high shear adhesion strength.
On the other hand, the X-ray absorption spectrum of the test piece OO did not show a peak indicating the presence of SH groups or SOx groups.
From the above results, it can be understood that even in the photocurable silicone composition not containing the component (D), the SOx group can be formed in the silicone gel by curing the silicone composition using an energy ray having high energy such as ultraviolet light irradiated from a high-pressure mercury lamp and then heating the obtained silicone gel.
(reference example)
This example is an example of evaluating the water repellency using a test body simulating the above-described waterproof case. In this example, first, the waterproof box 102 having the same form as that of embodiment 2 is prepared. The material of the box main body 2 and the lid 3 is PA 66. The sealing material holding groove 26 provided in the cartridge main body portion 2 had a width of 4.0mm and a depth of 2.2 mm. Further, the lid portion 302 is formed with a protrusion 33 having a height of 1.5 mm.
The sealing material 4 made of silicone rubber obtained by curing the composition E is disposed in the sealing material holding groove 26.
The silicone composition had a coating width of 3.0mm and a coating height of 1.7. + -. 0.2 mm. Thereafter, the silicone composition was irradiated with a cumulative light amount of 4500mJ/cm2The silicone composition is cured to form the sealing material 4. Coating width and coating height Hi of sealing material 4 and siliconeThe coating width and the coating height of the composition were the same.
Thereafter, the lid portion 302 is attached to the case body portion 2 by locking the engaging convex portion 23 to the receiving portion 31 while the protruding portion 33 is pressed into the sealing material 4. Thus, a test piece R1 was prepared. The height Hf of the sealing material 4 in the test piece R1 in the state in which the protrusion 33 was press-fitted was 0.4 ± 0.2 mm.
In this example, a test piece R2 having the same configuration as the conventional waterproof box 102 was prepared for comparison with the test piece R1. Although not shown in the figure, the test piece R2 has an O-ring as the sealing material 4 interposed between the case main body portion 2 and the lid portion 302, and has a structure in which the case main body portion 2 and the lid portion 302 are fastened by a bolt as a fastening member.
In this example, in order to compare with the test object R1, the seal material 4 in the test object R1 was replaced with an O-ring test object R3. However, the repulsive force from the O-ring is extremely high compared to the sealing material 4 made of silicone rubber. Therefore, in the process of pressing the lid portion 302 into the main body portion 2, the lid portion 302 is deformed at a timing when the compression ratio of the O-ring is about 50%, and the lid portion 302 and the main body portion 2 cannot be liquid-tightly sealed.
In the test pieces R1 and R2 having the above-described configurations, the pressure was applied so that the internal pressure of the storage space became 10 kPa. These test specimens were kept at a temperature of 130 ℃ and subjected to a high-temperature standing test. In addition, a cooling-heating cycle test was performed separately from the high-temperature standing test as follows: the cycle of holding the test body at a temperature of-30 ℃ for 30 minutes, followed by holding at a temperature of 100 ℃ for 30 minutes was repeated.
In the high-temperature standing test, the internal pressure of each test piece before the start of the test was maintained at a point when the retention time reached 187.5 hours. In the cold-hot cycle test, the internal pressure of each test piece before the start of the test was maintained at the time when the number of cycles reached 600 cycles.
From these results, it can be understood that the test piece R1 has a water-proof performance equal to or higher than that of the conventional water-proof box 102 using an O-ring. Further, by using organic silicone rubbers having SOx groups such as the test pieces AA to DD in the experimental example 1 and the test pieces II to JJ in the experimental example 2 as the sealing material 4 in the test piece R1, it is expected that the sealing material 4 is more strongly adhered to the box main body portion 2 and the lid portion 302, and the waterproof performance of the waterproof box 102 is further improved.
The present invention is not limited to the above embodiments, and can be applied to various embodiments without departing from the scope of the invention. For example, embodiment 1 and embodiment 2 show examples in which the engaging convex portion 23 is provided in the case main body portion 2 and the receiving portion 31 is provided in the cover portions 3 and 302, respectively, and the receiving portion may be provided in the case main body portion 2 and the engaging convex portion may be provided in the cover portions 3 and 302. Further, engaging convex portions may be provided on the case main body portion 2 and the lid portions 3 and 302, respectively, and receiving portions may be provided so as to correspond to these engaging convex portions.
The configuration of the engaging protrusion 23 and the receiving portion 31 is not limited to the embodiments of embodiment 1 and embodiment 2, and a configuration capable of realizing so-called snap-fit may be adopted. For example, the engaging convex portion may be locked to the receiving portion by press-fitting a pin as the engaging convex portion into a hole as the receiving portion.
The case main body 2 may be provided with a sealing material holding groove 26. That is, the sealing member 4 may be directly disposed at the front end 251 of the side wall portion 25, and the sealing surface of the cover portion 3 may compress the sealing member 4.
Further, the lid 3 may be provided with a sealant holding groove, and the sealant 4 may be disposed in the sealant holding groove.
The sealing material 4 in the waterproof case 1, 102 may be composed of 1 kind of silicone rubber. In this case, for example, the sealing material 4 made of a single type of silicone rubber may be formed by applying a single silicone composition to the portions of the case main body portion 2 and the lid portions 3 and 302 where the sealing material 4 is to be provided, and then curing the silicone composition.
The sealing material 4 may contain 2 or more kinds of silicone rubbers. In this case, for example, 2 types of the silicone compositions can be formed by coating the portions of the case main body portion 2 and the lid portions 3 and 302 to be provided with the sealing material 4 with silicone compositions having different compositions, respectively, and then curing these silicone compositionsThe sealing member 4 made of the above silicone rubber. In the sealing material 4 containing 2 or more kinds of silicone rubbers, the combination of the silicone rubbers is not particularly limited. For example, the sealing material 4 may contain a material selected from organic silica gel having SO groups and having adhesiveness, organic silica gel having SO groups2Organic silica gel having adhesive property, organic silica gel having SO3Organic silica gel with adhesive property, organic silica gel with SO group and SO2Organic silica gel with adhesive property, organic silica gel with SO group and SO3Organic silica gel having adhesive property, organic silica gel having SO2Radical and SO3Organic silicon glue with adhesive property, SO group and organic silicon oxide2Radical and SO3And 2 or more kinds of organic silica gels among the organic silica gels having adhesive properties.
Claims (14)
1. A waterproof box for an automobile, comprising:
a box main body portion having an accommodating space for accommodating an object to be accommodated and an opening communicating with the inside of the accommodating space;
a lid portion attached to the box main body portion and closing the opening;
a sealing material consisting of a material having an SO group or an SO group2Radical and SO3At least 1 SOx group of the bases and a silicone adhesive interposed between the case main body portion and the lid portion;
a receiving portion provided in at least one of the case main body portion and the lid portion; and
and an engaging projection provided at a position corresponding to the receiving portion in the case main body portion and the lid portion, and engaged with the receiving portion.
2. The automobile waterproof case according to claim 1, wherein the silicone rubber is a cured product of a photocurable silicone composition that contains a mercapto-based crosslinking agent having an SH group and an oxidizing agent that can oxidize the SH group and a thioether group.
3. The waterproof box for an automobile according to claim 1, wherein at least one of the box main body portion and the cover portion is made of resin.
4. The waterproof box for an automobile according to claim 1, wherein either the box main body portion or the lid portion is provided with a sealant holding groove having a bottom surface and a side surface continuous to the bottom surface, and the sealant is disposed on the bottom surface with a gap therebetween.
5. The waterproof box for an automobile according to claim 4, wherein a protrusion protruding toward the bottom surface is provided at a position facing the sealing material holding groove in the box main body portion and the lid portion, and the protrusion is press-fitted into the sealing material.
6. The waterproof box for an automobile as claimed in claim 1, wherein the sealing material is compressed so that a height Hf in a compressed state between the box main body portion and the lid portion becomes 40 to 80% of a height Hi in an uncompressed state.
7. The waterproof case for an automobile according to claim 1, used in an engine room of an automobile.
8. A photocurable organosilicon composition comprises the following components A-D, and can be formed into a composition having SO group or SO group2Radical and SO3At least 1 SOx group of the organic silica gel,
component A: a polyorganosiloxane having a vinylsiloxane group,
and B component: a mercapto-based crosslinking agent, a crosslinking agent,
and C, component C: a radical-based photoinitiator, which is a radical-based photoinitiator,
and (D) component: an organic peroxide having a 10-hour half-life temperature of 150 ℃ or less.
9. The photocurable silicone composition according to claim 8, wherein the component B is 0.1 to 10 parts by mass, the component C is 0.1 to 5.0 parts by mass, and the component D is 0.1 to 5.0 parts by mass, based on 100 parts by mass of the component A.
10. The photocurable silicone composition according to claim 8, wherein the component D is an organic peroxide having a peroxyester structure.
11. The photocurable silicone composition according to claim 10, wherein the component D has a molecular structure represented by the following general formula (1) or the following general formula (2),
R1－O－O－CO－R2a compound of the general formula (1),
R3－O－O－CO－O－R4a compound of the general formula (2),
wherein R in the general formula (1) and the general formula (2)1～R4Each independently a substituted or unsubstituted aromatic group, a hydrocarbon group selected from aliphatic hydrocarbon groups and unsaturated hydrocarbon groups.
12. The photocurable silicone composition according to claim 8, wherein the 10-hour half-life temperature of component D is 60 to 110 ℃.
13. The photocurable silicone composition according to claim 8, further comprising a filler as component E.
14. A silicone rubber obtained by curing the photocurable silicone composition according to any one of claims 8 to 13, wherein the silicone rubber has a structure selected from the group consisting of SO groups and SO groups2Radical and SO3At least 1 SOx group of the radicals.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020-077739 | 2020-04-24 | ||
| JP2020077739A JP2021174882A (en) | 2020-04-24 | 2020-04-24 | Waterproof case for automobile, photocurable silicone composition and silicone gel |
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| Publication Number | Publication Date |
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| CN113550824A true CN113550824A (en) | 2021-10-26 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1596382A (en) * | 2002-02-04 | 2005-03-16 | 三井化学株式会社 | Method for producing liquid crystal display cell and sealing agent for liquid crystal display cell |
| CN101098596A (en) * | 2006-06-29 | 2008-01-02 | 株式会社日立制作所 | Engine control device |
| CN104564342A (en) * | 2013-10-25 | 2015-04-29 | 本田技研工业株式会社 | Sound-insulating structure of internal combustion engine |
| CN107438650A (en) * | 2015-02-13 | 2017-12-05 | 凯密特尔有限责任公司 | The sealant and the method for curing by Photolatent catalysts of matrix polymer/epoxide based on sulfydryl end-blocking |
| CN113039382A (en) * | 2018-10-31 | 2021-06-25 | 株式会社电装 | Waterproof case for automobile |
-
2020
- 2020-04-24 JP JP2020077739A patent/JP2021174882A/en active Pending
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2021
- 2021-04-23 CN CN202110441570.4A patent/CN113550824A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1596382A (en) * | 2002-02-04 | 2005-03-16 | 三井化学株式会社 | Method for producing liquid crystal display cell and sealing agent for liquid crystal display cell |
| CN101098596A (en) * | 2006-06-29 | 2008-01-02 | 株式会社日立制作所 | Engine control device |
| CN104564342A (en) * | 2013-10-25 | 2015-04-29 | 本田技研工业株式会社 | Sound-insulating structure of internal combustion engine |
| CN107438650A (en) * | 2015-02-13 | 2017-12-05 | 凯密特尔有限责任公司 | The sealant and the method for curing by Photolatent catalysts of matrix polymer/epoxide based on sulfydryl end-blocking |
| CN113039382A (en) * | 2018-10-31 | 2021-06-25 | 株式会社电装 | Waterproof case for automobile |
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