JP2012047232A - Casing structure united with packing, and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a casing structure united with a packing that eliminates the work for mounting the packing and exhibits a sufficient sealing function by a low compression rate.SOLUTION: The structure includes: a case having a recessed groove continuous to a circumference part; a case having a protrusion continuous to the circumference part; and an elastic packing united to the inside of the recessed groove of the case having the recessed groove. In the structure united with the packing, the united elastic packing has a surface adhesiveness, and has the 90 ° peel strength to the case plate of at least 3 N/25 mm.

Description

  In order to prevent water and dust from entering the inside of the housing, the present invention provides a housing having a concave groove continuous to the peripheral portion, a housing having a convex portion continuous to the peripheral portion, and a concave groove. A housing integrated with the packing, characterized by having an elastic packing integrated in the concave groove of the housing, and sealing the inside of the housing by pressing the elastic packing by fitting the concave groove and the convex portion. The present invention relates to a body structure and a manufacturing method.

In recent years, small portable electronic devices represented by mobile phones, mobile PCs, MP3 players, digital video recorders, digital cameras, etc. have improved performance such as increased processing speed and increased recording capacity, as well as communication functions and games via the Internet. Multi-functionality such as functions, music / image file import and playback functions, etc. is rapidly progressing. In addition, products that are easier to carry, such as smaller, thinner, and lighter, have been developed, and the frequency of outdoor use is increasing. It has become important. Portable electronic devices themselves are pursuing their portability and are becoming lighter and thinner. Therefore, it is desired that the width of the housing groove in which the packing is disposed is narrow, and the width is narrow and the thickness is reduced in the same manner as the corresponding packing in the direction of decreasing the depth. In addition to these required characteristics, in order to provide a waterproof function, it has been studied in a combined manner including the optimization of the packing and gasket shape inserted into the housing split part. For example, Patent Document 1 discloses a technique for waterproofing a casing division part of an electronic device using a gasket having an irregular cross section (Patent Document 1).
However, since the packing has no self-holding shape, there is a drawback in that workability for mounting the packing in the concave groove of the housing is poor. In order to solve the problem regarding the mounting property, a method of directly forming a packing in the housing groove itself has been considered. For example, a liquid material is applied and cured by an automatic application device and used as a packing. A method of applying a liquid gasket to one flange, curing the liquid gasket, and then compressing the gasket by narrowing the gap between both flanges and sealing the repulsive force has been known for a long time (Patent Document 2). ). Further, as such a liquid material, a gasket type used for a seal part of a precision instrument or an electronic instrument, which has a multi-stage cross section using an ultraviolet curable elastomer, is exemplified (patent) Reference 3).

  However, it is extremely difficult to obtain a uniform shaped packing by a method of applying and curing these liquid materials to obtain a packing. In particular, in the case of a packing having a small shape, it is difficult to control the thickness at the corner portion and the overlapping portion. In the conventional seal design using the high repulsive force of the packing, this thickness unevenness is a very important problem, and in the case of a thin packing, it is difficult to ensure a stable sealing performance.

JP 2008-218633 A JP-A-62-77597 Japanese Patent Laid-Open No. 2003-120819

  However, conventional packings and gaskets are made of rubber-elastic material, and in the environment of use, they use a repulsive force when compressed to a certain ratio to express a sealing function such as waterproofness. Due to the structure of the housing, for example, it is difficult to apply the minimum compression rate and compressive force necessary to develop waterproofness over the entire circumference of the packing due to the thinning of the product and the thinning of the housing. There is a problem that the waterproofness cannot be maintained because sufficient repulsive force cannot be obtained due to deterioration of the material. Further, since the packing does not have a shape self-holding property, there is a disadvantage that workability for mounting the packing in the concave groove of the housing is poor.

  The present invention has been made to solve the above-described problems, and provides a housing structure that is integrated with a packing that exhibits waterproof performance even under a low compression ratio and compression force and eliminates the packing mounting operation. The purpose is to do.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that excellent waterproof performance is exhibited even at a low compression rate by imparting adhesiveness to the packing, and a casing and manufacturing integrated with the packing It came to invent the method.

That is, the present invention
A structure having a housing having a concave groove continuous to the peripheral portion, a housing having a convex portion continuous to the peripheral portion, and an elastic packing integrated in the concave groove of the housing having the concave groove. A casing structure integrated with a packing, characterized in that the formed elastic packing has surface adhesiveness, and the 90 ° peel strength with respect to the casing plate is 3 N / 25 mm or more.
The housing structure integrated with the packing is characterized in that the hardness of the elastic packing measured according to JIS K6253 is JIS hardness 40A or less.
Also, a housing structure integrated with a packing, characterized in that a thermosetting liquid resin composition is injected into a cavity formed when a housing having a concave groove at its peripheral edge is inserted into a mold and clamped It is a manufacturing method of a body.
A casing structure integrated with a packing, wherein a tab is provided at a position avoiding a fitting portion between the concave groove and the convex portion, and the tab has a pin gate of φ0.8 or less. It is a manufacturing method.
Further, the present invention is a method for manufacturing a housing structure integrated with a packing, characterized in that a tab is provided at a position where the material is injected from the pin gate.
Moreover, it is the housing | casing structure integrated with the packing whose width | variety of the concave groove formed in the housing | casing peripheral part is 1 mm or less and whose depth is 1 mm or less.
A casing structure integrated with a packing, wherein a taper is formed at an opening of a concave groove formed at a peripheral edge of the casing, and a fixed mold is pressed against the tapered portion. It is a manufacturing method.
In addition, the curable liquid resin composition contains the following components (A) to (C), and the housing structure (A) integrated with the packing is characterized in that it is at least one in one molecule. Organic polymer (B) having a number average molecular weight of 1,000 to 50,000 having an alkenyl group in excess of Compound (C) Compound having at least two hydrosilyl groups in one molecule (C) Hydrosilylation catalyst A) is at least one selected from (a-1) a saturated hydrocarbon polymer, (a-2) a polyoxyalkylene polymer, and (a-3) a poly (meth) acrylic polymer. Housing structure integrated with packing,
About.

  The present invention provides a housing structure that is integrated with a packing having a good waterproof performance even at a low compression rate, by omitting the packing mounting operation and imparting adhesiveness to the packing.

FIG. 1 is a shape diagram of a housing structure integrated with a packing according to an embodiment of the present invention. FIG. 2 is a cross-sectional view of the packing member shown in FIG. 1 according to an embodiment of the present invention. Drawing 3 is a mimetic diagram of a manufacturing method of a housing structure integrated with packing of one embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail.
FIG. 1 is a shape diagram of a housing structure integrated with a packing.
A concave groove is formed in the peripheral edge of the housing 1, and an elastic packing having adhesiveness is integrated in this groove. On the other hand, the peripheral shape of the housing 2 is provided with a convex shape, and the elastic packing is compressed by fitting the housing 1 and the housing 2 together. The tip shape of the projecting portion for compressing the packing is a hemispherical shape, but is not limited thereto. However, from the viewpoint of the stress applied to the packing, a hemispherical shape having no corner at the tip of the protrusion is preferable because it is easy to avoid local stress concentration. The compression ratio of the packing is 5 to 30%, more preferably 8 to 25%. When the compression ratio is large, the sealing performance is improved, but it is necessary to increase the strength of the casing due to the compressive stress, which is not preferable for thinning the casing structure. Further, if the compression rate is too small, waterproof performance is not guaranteed.

  As the material of the casing, in addition to metal, resins such as polycarbonate, polycarbonate / ABS, nylon, and PBT are often used. Specifically, the adhesive strength of the elastic packing is preferably 90 N peel adhesive strength (23 ° C., against housing material plate), preferably 3 N / 25 mm or more. The hardness of the packing elastic body is specifically 60A or less, preferably 40A or less in terms of JIS hardness measured according to JIS K6253.

  Examples of the manufacturing method of the casing structure in which the packing is integrated include dispense coating, press molding, transfer molding, and injection molding. However, since precise processing without flash is required, injection molding is preferable. A casing structure integrated with the packing is obtained by inserting a casing having a concave groove in the peripheral portion into a movable side mold for injection molding and injecting a packing material into a cavity formed when the mold is clamped. . The packing material is preferably a liquid thermosetting resin composition from the viewpoint of compression set and durability, and the injection property of the material. The casing 1 is inserted into the heated mold, and a liquid thermosetting resin composition is injected and simultaneously cured to form an elastic packing.

  The injection gate is preferably provided with a tab at a position avoiding the concave groove and the convex fitting portion, and the tab is injected from a pin gate of φ0.8 or less. The size of the tab preferably has an area corresponding to φ0.5 to φ2. The shape may be circular or rectangular. If a gate is provided in the fitting portion, a minute step is formed in the gate portion, so that sealing performance is not guaranteed. The gate size is preferably φ1 or less, more preferably φ0.8. Exceeding φ1 is not preferable because it affects the storage of electronic components installed inside the housing.

  Moreover, it is preferable to provide a tab for injecting air at the position where the liquid curable resin composition is injected from the pin gate and this material joins. If this tab is not provided, air tends to remain at the junction, causing a seal failure.

  The dimensions of the concave groove formed on the peripheral edge of the housing 1 are preferably 1 mm or less in width and 1 mm or less in depth. If the width and depth exceed 1 mm, the demand for thinning and miniaturization cannot be answered. The thickness of the housing structure is preferably 10 mm or less.

  Further, a structure in which a taper is formed on the opening surface of the concave groove formed on the peripheral edge of the housing, and a fixed-side mold is pressed against the taper is preferable. By being in pressure contact with the tapered portion, the casing and the mold can be easily sealed, and integral molding without flash is possible. The taper angle is preferably 5 to 45 °. When the taper angle is 5 ° or less, the biting and releasability becomes worse when the fixed mold is pressed. If it exceeds 45 °, the sealing performance is lowered and burrs are likely to occur.

  Specific curable compositions capable of forming an elastic packing having adhesive properties include (A) an organic polymer having more than one alkenyl group in one molecule, and (B) an average of two in one molecule. Examples thereof include a compound having an excess hydrosilyl group and a composition comprising (C) a hydrosilylation catalyst as an essential component.

  In the component (a-1) in the present invention, the alkenyl group capable of undergoing hydrosilylation reaction may be present at the main chain end or side chain of the saturated hydrocarbon polymer, or may be present in both. In particular, when the alkenyl group is at the end of the main chain, the effective network chain amount of the saturated hydrocarbon polymer component contained in the finally formed cured product increases, so that the rubber-like curing with high strength and high elongation is achieved. It is preferable from the standpoint that a product is easily obtained.

  (A-1) The polymer constituting the skeleton of the saturated hydrocarbon polymer of component (1) is mainly composed of an olefinic compound having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene, isobutylene and the like. It can be obtained by a method such as polymerizing, (2) homopolymerizing a diene compound such as butadiene or isoprene, or copolymerizing the olefin compound and the diene compound and then hydrogenating. However, isobutylene-based polymers, hydrogenated polybutadiene-based polymers or hydrogenated polyisoprene-based polymers are easy to introduce functional groups at the ends, easily control the molecular weight, and increase the number of terminal functional groups. A polymer is preferred.

  In the isobutylene polymer, all of the monomer units may be formed from isobutylene units, and the monomer units having copolymerizability with isobutylene are preferably 50% by weight or less in the isobutylene polymer, The content may be preferably 30% by weight or less, particularly preferably 20% by weight or less.

  Examples of such monomer components include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, allyl silanes, and the like. Specific examples of such copolymer components include 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, Vinylcyclohexane, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methyl styrene, dimethyl styrene, pt-butoxy styrene, p-hexenyloxy styrene, p-allyloxy styrene, p-hydroxy styrene , Β-pinene, indene, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane Allyldimethylmethoxysilane, Examples include allyltrimethylsilane, diallyldimethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropylmethyldimethoxysilane. Particularly preferably, all of the monomer units are formed from isobutylene units.

  The hydrogenated polybutadiene polymer and other saturated hydrocarbon polymers also contain other monomer units in addition to the main monomer unit as in the case of the isobutylene polymer. You may let them.

  Further, in the saturated hydrocarbon polymer used as the component (a-1) in the present invention, butadiene, isoprene, 1,13-tetradecadiene, 1,9-decadiene, as long as the object of the present invention is achieved, A monomer unit such as a polyene compound such as 1,7-octadiene and 1,5-hexadiene, which remains a double bond after polymerization, may be contained in a small amount, preferably in the range of 10% by weight or less.

  As the method for producing the component (a-1) of the present invention, an unsaturated group is added to a polymer having a functional group such as a hydroxyl group as disclosed in JP-A-3-152164 and JP-A-7-304969. The method which introduce | transduces an unsaturated group into a polymer by making the compound which has it react is raised. In addition, to introduce an unsaturated group into a polymer having a halogen atom, a method of performing a Friedel-Crafts reaction with an alkenylphenyl ether, a method of performing a substitution reaction with allyltrimethylsilane in the presence of a Lewis acid, various phenols and Friedel For example, a method in which the above alkenyl group introduction method is used in combination with the introduction of a hydroxyl group by carrying out a kraft reaction. Furthermore, a method of introducing an unsaturated group at the time of polymerization of a monomer as disclosed in US Pat. No. 4,316,973, Japanese Patent Laid-Open No. 63-105005, and Japanese Patent Laid-Open No. 4-288309 is also possible.

  The alkenyl group should be present in an amount exceeding 1 on average, preferably 5 or less on average in one molecule of the polymer (a-1). More preferably, it is 1.2 or more and 3 or less. When the number of alkenyl groups contained in one molecule of the polymer (a-1) is 1 or less on average, the curability becomes insufficient and the resulting network structure is incomplete, and a good molded product is obtained. I can't get it. Further, when the number of alkenyl groups contained in one molecule increases, the network structure becomes too dense, so that the resulting molded product is hard and brittle, which is not preferable. In particular, when the number is 5 or more, the tendency becomes remarkable.

There is no restriction | limiting in particular as a polyoxyalkylene type polymer which has more than 1 alkenyl group in 1 molecule which is (a-2) component of this invention, A well-known thing is mention | raise | lifted. Specifically, the main chain skeleton of the polymer has a repeating unit represented by the general formula (1).
General formula (1):
—R ¹ —O— (1)
(Wherein R ¹ is a divalent alkylene group)

R ¹ in the general formula (1) is not particularly limited as long as it is a divalent alkylene group. Among them, an alkylene group having 1 to 14 carbon atoms is preferable, and a linear or branched chain having 2 to 4 carbon atoms. The alkylene group is more preferable. The repeating unit of the general formula (1) wherein, not particularly limited, for _{example, -CH 2 O -, - CH} 2 CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C _{2 H 5) O -, -} CH 2 C (CH 3) 2 O -, - CH 2 CH 2 CH 2 CH 2 O- and the like.

The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit or may be a combination of a plurality of repeating units. Among these, a polymer composed of —CH ₂ CH (CH ₃ ) O— as the main repeating unit is preferable because it is easily available and has excellent workability. In addition, a repeating unit other than the oxyalkylene unit may be contained in the main chain skeleton of the polymer. In this case, the total proportion of oxyalkylene units contained in the polymer is preferably 80% by weight or more, particularly 90% by weight or more.

  The main chain skeleton of the polymer of component (a-2) may be a linear polymer, a branched polymer, or a mixture thereof. Among these, in order to obtain good elasticity, it is preferable to contain 50% by weight or more of a linear polymer.

  The number average molecular weight of the polymer of component (a-2) is preferably 1,000 to 100,000, and more preferably 1,000 to 50,000. When the number average molecular weight is less than 1,000, the resulting crosslinked rubber has a high elastic modulus. Conversely, when the number average molecular weight exceeds 50,000, the viscosity tends to be high and the handling of the composition tends to be significantly reduced. The number average molecular weight can be measured by various methods, but is usually measured by conversion from a terminal group analysis of a polyoxyalkylene polymer or a gel permeation chromatography (GPC) method.

The alkenyl group in the component (a-2) is not particularly limited, and examples thereof include known alkenyl groups. Among these, an alkenyl group represented by the following general formula (2) is preferable. General formula (2):
^{_{H 2 C = C (R 2}} ) - (2)
(In the formula, R ² is hydrogen or a methyl group.)

  The bonding mode of the alkenyl group to the polyoxyalkylene polymer is not particularly limited, and examples thereof include a direct bond of an alkenyl group, an ether bond, an ester bond, a carbonate bond, a urethane bond, and a urea bond.

As a polymer of the component (a-2), the general formula (3):
_{^{{H 2 C = C (R}} 3) -R 4 -O} a -R 5 (3)
(In the formula, R ³ is hydrogen or a methyl group. R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms, and one or more ether groups may be contained therein. R ⁵ is an initiator residue of a polyoxyalkylene polymer, and a is a positive integer). R ⁴ described in the general formula (3) is not particularly limited. For example, —CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) CH _2- , —CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ OCH ₂ CH ₂ —, —CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ — and the like can be mentioned. Among these, —CH ₂ — is preferable because synthesis is easy.

Other than the above, the polymer of the component (a-2) is represented by the general formula (4):
_{^{{H 2 C = C (R}} 3) -R 4 -OC (= O)} a -R 5 (4)
(Wherein R ³ , R ⁴ , R ⁵ and a are the same as those in the general formula (3)), and a polymer having an ester bond.

Moreover, general formula (5):
^{_{{H 2 C = C (R}} 3)} a -R 5 (5)
(In formula, R < ³ >, R < ⁵ > and a are the same as the description of General formula (3), (4)), and the polymer shown is also mentioned. Furthermore, the following general formula (6):
^{_{{H 2 C = C (R}} 3) -R 4 -OC (= O) O} a -R 5 (6)
A polymer having a carbonate bond represented by the formula (wherein R ³ , R ⁴ , R ⁵ and a are the same as those in the general formulas (3), (4) and (5)) is also included.

  The polymerization method of the polyoxyalkylene polymer (a-2) is not particularly limited. For example, a normal polymerization method of oxyalkylene disclosed in JP-A-50-13396 (an anion using caustic alkali) Polymerization method), a polymerization method based on a chain extension reaction method using a polymer obtained by the anionic polymerization method disclosed in JP-A-50-149797 and the like, disclosed in JP-A-7-179597, etc. Porphyrin / aluminum complex catalysts disclosed in JP-A 61-197631, JP-A 61-215622, JP-A 61-215623, and JP-A 61-218632 A polymerization method using a double metal cyanide complex catalyst disclosed in JP-B-46-27250 and JP-B-59-15336 Polymerization method, polymerization method using a catalyst comprising a polyphosphazene salt disclosed in JP-A 10-273512 Patent and the like.

  Among these, a polymerization method using a double metal cyanide complex catalyst is preferable because of its high practicality, easy availability of the catalyst, and stable polymer production. The production method of the double metal cyanide complex catalyst is not particularly limited, and examples thereof include known methods. For example, U.S. Pat. Nos. 3,278,457, 3,278,459, and 5,891,818. 5,767,323, 5,767,323, 5,536,883, 5,482,908, 5,158,922, 4,472,560, 6,063,897, 5,891,818, 5,627,122, 5,482,908, 5,470,813, 5,158,922, etc. The manufacturing method is preferred.

  The method for introducing an alkenyl group into the polyoxyalkylene polymer is not particularly limited and includes known methods. For example, a method by copolymerization of a compound having an alkenyl group such as allyl glycidyl ether and an oxyalkylene compound. Can be given. Further, the method for introducing an alkenyl group into the main chain or side chain is not particularly limited. And a method of reacting an organic compound having a functional group and an alkenyl group having reactivity with respect to. A curable composition containing a polymer in which an alkenyl group is present at the end of the main chain of the polymer is preferable because the resulting cured product has a large effective network chain length and is excellent in mechanical properties.

  The organic compound having a functional group having reactivity with a functional group such as a hydroxyl group or an alkoxide group and an alkenyl group is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, vinyl acetate, acrylic acid chloride, and acrylic acid bromide. Acid halides, anhydrides, allyl chloroformates, allyl chlorides, allyl bromides, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, Examples include allyl (chloromethyl) ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy) benzene, allyloxy (chloromethyl) benzene, and the like.

  The number of alkenyl groups present in one molecule of the polymer as component (a-2) is preferably more than 1 and not more than 5. When the number of alkenyl groups present in one molecule of the polymer (A) is 1 or less, the curable composition tends to be insufficiently cured, and the resulting cured product has an incomplete network structure. Therefore, there is a tendency that a good molded product cannot be obtained. Moreover, when the alkenyl group which exists in 1 molecule of polymer (a-2) increases, since the network structure of the hardened | cured material obtained becomes too dense, a molded object tends to become hard and brittle. In particular, when the number is 5 or more, the tendency becomes remarkable.

The poly (meth) acrylic polymer having at least one average alkenyl group in one molecule, which is the component (a-3) of the present invention, preferably has a molecular weight of 1,000 to 50,000. The main chain is preferably a polymer produced mainly by polymerizing a (meth) acrylic monomer. Here, “mainly” means that 50 mol% or more of the monomer units constituting the main chain is the above monomer, and preferably 70 mol% or more.
Among these, from the physical properties of the product, (meth) acrylic acid monomers are preferable, acrylic ester monomers and / or methacrylic ester monomers are more preferable, and acrylic ester monomers are more preferable. Particularly preferred acrylic ester monomers include alkyl acrylate monomers, specifically ethyl acrylate, 2-methoxyethyl acrylate, stearyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic acid. 2-methoxybutyl.

  In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in this case, these preferred monomers may be contained in a weight ratio of 40% by weight or more. preferable.

  The molecular weight distribution of the poly (meth) acrylic polymer (a-3) in the present invention, that is, the ratio (Mw) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC). / Mn) is not particularly limited, but is preferably less than 1.8, more preferably 1.7 or less, still more preferably 1.6 or less, even more preferably 1.5 or less, Particularly preferred is 1.4 or less, and most preferred is 1.3 or less. If the molecular weight distribution is too large, the viscosity at the molecular weight between the same cross-linking points increases and the handling tends to be difficult. In the GPC measurement in the present invention, chloroform is used as the mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

  The number average molecular weight of the poly (meth) acrylic polymer (a-3) in the present invention is 1,000 to 100,000, more preferably 1,000 to 50,000. When the number average molecular weight is less than 1,000, the resulting crosslinked rubber has a high elastic modulus. Conversely, when the number average molecular weight exceeds 50,000, the viscosity tends to be high and the handling of the composition tends to be significantly reduced.

  The poly (meth) acrylic polymer (a-3) in the present invention can be obtained by various polymerization methods, and is not particularly limited. However, radical polymerization methods can be used from the viewpoint of versatility of the monomers and ease of control. Among the radical polymerizations, controlled radical polymerization is more preferable. This controlled radical polymerization method can be classified into a “chain transfer agent method” and a “living radical polymerization method”. Living radical polymerization that allows easy control of the molecular weight and molecular weight distribution of the poly (meth) acrylic polymer (a-3) to be obtained is more preferable, because of availability of raw materials and ease of introduction of functional groups at the polymer ends. Atom transfer radical polymerization is particularly preferred. The radical polymerization, controlled radical polymerization, chain transfer agent method, living radical polymerization method, and atom transfer radical polymerization are known polymerization methods. For example, JP-A-2005-232419 and JP-A-2005-234419 The description of 2006-291073 gazette etc. can be referred to.

  Atom transfer radical polymerization, which is one of preferred synthesis methods of the poly (meth) acrylic polymer (a-3) in the present invention, will be briefly described below.

  In atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl-position), or a sulfonyl halide. A compound or the like is preferably used as an initiator. Specific examples include compounds described in paragraphs [0040] to [0064] of JP-A-2005-232419.

  In order to obtain a vinyl polymer having more than one alkenyl group in one molecule, an organic halide having two or more starting points or a sulfonyl halide compound is preferably used as an initiator. Specific examples include the following compounds.

  There is no restriction | limiting in particular as a (meth) acrylic-acid type monomer used in atom transfer radical polymerization, All the (meth) acrylic-acid type monomers illustrated above can be used suitably.

  Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses periodic group 7th group, 8th group, 9th group, 10th group, or 11 group element as a central metal, More preferably Examples include transition metal complexes having zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel as a central metal, particularly preferably a copper complex. Specific examples of the monovalent copper compound used to form the copper complex include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, and oxidized oxide. Cuprous, cuprous perchlorate, and the like. In the case of using a copper compound, 2,2′-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity These polyamines are added as ligands.

The polymerization reaction can be carried out without solvent, but can also be carried out in various solvents. It does not specifically limit as a kind of solvent, The solvent of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0067] is mentioned. These may be used alone or in combination of two or more. Polymerization can also be performed in an emulsion system or a system using supercritical fluid CO ₂ as a medium.

  Although superposition | polymerization temperature is not limited, It can carry out in the range of 0-200 degreeC, Preferably, it is the range of room temperature-150 degreeC.

(A-3) Although it does not specifically limit as an alkenyl group in a component, It is preferable that it is what is represented by General formula (7).
H ₂ C═C (R ⁶ ) − (7)
(In the formula, R ⁶ represents hydrogen or an organic group having 1 to 20 carbon atoms.)

The organic group having 1 to 20 carbon atoms of the ^{R 6,} are not particularly limited, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms include preferably Specifically, the following groups are exemplified.
_{- (CH 2) n -CH 3} , -CH (CH 3) - (CH 2) n -CH 3, -CH (CH 2 CH 3) - (CH 2) n -CH 3, -CH (CH 2 CH _{3) 2, -C (CH 3} ) 2 - (CH 2) n -CH 3, -C (CH 3) (CH 2 CH 3) - (CH 2) n -CH 3, -C 6 H 5, - _{C 6 H 4 (CH 3)} , - C 6 H 3 (CH 3) 2, - (CH 2) n -C 6 H 5, - (CH 2) n -C 6 H 4 (CH 3), - ( _{CH 2) n -C 6 H 3} (CH 3) 2
(N is an integer of 0 or more, and the total carbon number of each group is 20 or less)
From the viewpoint of the activity of the hydrosilylation reaction that is the crosslinking reaction of the present invention, R ⁶ is more preferably hydrogen or a methyl group.

  The alkenyl group of the poly (meth) acrylic polymer (a-3) is not particularly limited, but is not activated by a carbonyl group, an alkenyl group or an aromatic ring conjugated with the carbon-carbon double bond. Is preferred.

  The bonding mode between the alkenyl group and the main chain of the poly (meth) acrylic polymer is not particularly limited, but is bonded through a carbon-carbon bond, an ester bond, an ether bond, a carbonate bond, an amide bond, a urethane bond, or the like. It is preferable.

The poly (meth) acrylic polymer (a-3) has more than one alkenyl group in one molecule, and one molecule of poly (meth) acrylic polymer from the viewpoint of mechanical properties of the cured product. Those having an average of 1.2 to 3.0 are preferred. Although not particularly limited, specifically, the average value obtained by ¹ H-NMR analysis of the number of alkenyl groups introduced per molecule of the poly (meth) acrylic polymer is 1.2 to 3 The number is preferably 0.0, and more preferably 1.5 to 2.5.

  When rubber properties are particularly required for the cured product obtained from the curable composition of the present invention, the molecular weight between crosslinking points that greatly affects rubber elasticity can be increased, so that at least one of the alkenyl groups is a molecule. It is preferably at the end of the chain (main chain). More preferably, it has all alkenyl groups at the molecular chain ends.

  The poly (meth) acrylic polymerization having more than one alkenyl group at the molecular end is disclosed in JP-B-3-14068, JP-B-4-55444, JP-A-6-221922, and the like. It can be manufactured by a method. However, since these methods are free radical polymerization methods using the above-mentioned “chain transfer agent method”, the resulting polymer has a relatively high proportion of alkenyl groups at the molecular chain ends, while the molecular weight distribution (Mw / Mn) generally has a large value of 2 or more, resulting in a problem of increased viscosity. Therefore, in order to obtain a poly (meth) acrylic polymerization having a narrow molecular weight distribution and a low viscosity and having a high proportion of alkenyl groups at the molecular chain ends, the above-mentioned “living radical weight” is used. It is preferable to use “legal method”.

  As a method for introducing an alkenyl group into the obtained poly (meth) acrylic polymerization, a known method can be used. For example, the method of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0074]-[0099] is mentioned. Among these methods, the diene compound addition method is preferable because it is easier to control. When obtained from poly (meth) acrylic polymerization containing at least one hydroxyl group in the molecule, a method of reacting alkenyl alcohol at the end of the polymerization from the viewpoint of easier control, stabilized carbanion at the reaction terminal of the polymer It is preferable to use a vinyl polymer obtained by a method of reacting at least one hydroxyl group in the molecule.

  Here, a diene compound addition method, which is one of preferable introduction methods, will be briefly described below. The diene compound addition method is a compound having at least two alkenyl groups with low polymerizability in poly (meth) acrylic polymerization obtained by living radical polymerization of (meth) acrylic monomers (hereinafter referred to as “diene compound”). React.

Examples of the alkenyl group of the diene compound include a terminal alkenyl group [CH ₂ ═C (R) —R ′; R is hydrogen or an organic group having 1 to 20 carbon atoms, and R ′ is a monovalent or divalent one having 1 to 20 carbon atoms. R and R ′ may be bonded to each other to have a cyclic structure. ] Or an internal alkenyl group [R′—C (R) ═C (R) —R ′; R is hydrogen or an organic group having 1 to 20 carbon atoms, R ′ is a monovalent or divalent group having 1 to 20 carbon atoms It is an organic group, and two R or two R ′ may be the same or different from each other. Any two of two R and two R ′ may be bonded to each other to have a cyclic structure. ], But a terminal alkenyl group is more preferable. R is hydrogen or an organic group having 1 to 20 carbon atoms, and examples of the organic group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms. The aralkyl group is preferably. Among these, as R, hydrogen or a methyl group is particularly preferable. Examples of the monovalent or divalent organic group having 1 to 20 carbon atoms of R ′ include a monovalent or divalent alkyl group having 1 to 20 carbon atoms, a monovalent or divalent aryl group having 6 to 20 carbon atoms, A monovalent or divalent aralkyl group having 7 to 20 carbon atoms is preferred. Among these, R ′ is particularly preferably a methylene group, an ethylene group, or an isopropylene group. At least two alkenyl groups of the diene compound may be the same or different from each other, and at least two alkenyl groups of the diene compound may be conjugated.

  Specific examples of the diene compound include isoprene, piperylene, butadiene, myrcene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene, etc. 5-hexadiene, 1,7-octadiene and 1,9-decadiene are preferred.

  Living radical polymerization of (meth) acrylic monomer is performed, and the obtained polymer is isolated from the polymerization system, and then the isolated polymer and the diene compound are subjected to a radical reaction to form an alkenyl group at the target terminal. Although it is possible to obtain poly (meth) acrylic polymerization, it is easy to add a diene compound into the polymerization reaction system at the end of the polymerization reaction or after completion of the reaction of the predetermined (meth) acrylic monomer. More preferred.

  The addition amount of the diene compound may be an equivalent amount or a small excess amount with respect to the polymer growth terminal when the diene compound having a large difference in reactivity between the two alkenyl groups is used. When using a diene compound having the same or little difference in properties, it is preferably an excess amount relative to the polymer growth terminal, specifically preferably 1.5 times or more, more preferably 3 times or more, particularly Preferably it is 5 times or more.

  As the poly (meth) acrylic polymer (a-3) used in the curable composition of the present invention, among the above-described production methods, those obtained by the following method are particularly suitable.

As the first method,
(1a) By polymerizing a (meth) acrylic monomer by an atom transfer radical polymerization method, the following general formula (8)
^{-C (R 7) (R 8} ) (X) (8)
(In the formula, R ⁷ and R ⁸ represent a group bonded to an ethylenically unsaturated group of the (meth) acrylic monomer. X represents chlorine, bromine or iodine.)
A poly (meth) acrylic polymer having a terminal structure represented by
(2a) converting the terminal halogen of the polymer into a substituent having an alkenyl group;
A method is mentioned.

As a second method,
(1b) A poly (meth) acrylic polymer is produced by polymerizing a (meth) acrylic monomer by a living radical polymerization method,
(2b) reacting the polymer with a compound having at least two low-polymerizable alkenyl groups;
A method is mentioned.

  The compound having at least two hydrosilyl groups in one molecule as the component (B) in the present invention is not particularly limited as long as it has two hydrosilyl groups, and among these, it is easy to obtain raw materials. In view of good compatibility with the component (A), organohydrogenpolysiloxane modified with an organic group is preferred. The number of hydrosilyl groups in component (B) is 2 or more, preferably 3 or more, and the upper limit is preferably 40 or less and 20 or less.

  As the organohydrogenpolysiloxane, a known chain or cyclic organohydrogenpolysiloxane can be used, and from the viewpoint of compatibility with the component (A), an aromatic ring-containing chain or cyclic organohydrogen. Siloxane is preferred. Specific examples thereof include hydrosilyl group-containing compounds described in paragraphs [0088] to [0093] of JP-A-2006-291073.

  A linear or cyclic organohydrogenpolysiloxane in which a part of the hydrosilyl group is substituted with a low molecular weight compound having two or more alkenyl groups in the molecule can also be used. Specifically, a modified hydrosilyl group obtained by slowly dropping a low molecular compound having two or more alkenyl groups in the molecule in the presence of a hydrosilylation catalyst described later with respect to an excessive amount of the above hydrosilyl group-containing compound. The containing compound can be used as the hydrosilyl group-containing compound (B). Examples of the low molecular compound having two or more alkenyl groups in the molecule include aliphatic hydrocarbon compounds, ether compounds, ester compounds, carbonate compounds, isocyanurate compounds and aromatic hydrocarbon compounds. Specifically, compounds described in paragraph [0094] of JP-A-2006-291073 can be used. Among such modified hydrosilyl group-containing compounds, the following are considered in consideration of the availability of raw materials, the ease of removal of excessively used hydrosilyl group-containing compounds, and the compatibility with (A). Preferably mentioned.

  The amount of the compound having a hydrosilyl group as the component (B) in the present invention is the amount of the alkenyl group present in the polymer of the component (A) and the amount of the hydrosilyl group present in the compound in the component (B). In relation to the amount, it is selected as appropriate, and in the curable composition of the present invention, the above-mentioned compound having a hydrosilyl group may be used alone or in combination of two or more.

  In the present invention, the amount of the hydrosilyl group-containing compound that is the component (B) is such that [total amount of hydrosilyl groups in the component (B)] / [total amount of alkenyl groups in the component (A)] is 0.5 or more. It is preferably 5 or less, more preferably 0.7 or more and 2.0 or less. When [total amount of hydrosilyl groups in component (B)] / [total amount of alkenyl groups in component (A)] is less than 0.5, the resulting cured product has low crosslink density and therefore exhibits rubber elasticity. It becomes difficult.

The hydrosilylation catalyst which is component (C) of the present invention is not particularly limited, and examples thereof include known ones. For example, solid platinum is supported on a carrier such as chloroplatinic acid, platinum alone, alumina, silica, carbon black and the like. Platinum-vinylsiloxane complex {eg, Pt _X (ViMe ₂ SiOSiMe ₂ Vi) _y , Pt [(MeViSiO) ₄ ] _z }; Platinum-phosphine complex {eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ }; platinum-phosphite complex {eg, Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ (wherein Me is a methyl group, Bu is a butyl group, and Vi is a vinyl group) , Ph represents a phenyl group, x, y, z are integers), Pt _{(acac) 2} (However, acac represents acetylacetonato), also, Ashby Platinum is disclosed in U.S. Pat. No. 3159601 and 3159662 - hydrocarbon complexes, and platinum alcoholate catalysts may also be mentioned that disclosed in Lamoreaux et al. U.S. Pat. No. 3,220,972.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl _{4 and the} like.

These catalysts may be used alone or in combination. Among the above catalysts, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes, Pt (acac) _{2 and the} like are preferable because of their high catalytic activity.
Although there is no restriction | limiting in particular as the usage-amount of a catalyst (C), 10 ^{< -8} > -10 ^{< -1} > mol is preferable with respect to ¹ mol of alkenyl groups in (A) component, and 10 ^{< -6} > -10 ^<-2 > mol is more preferable. . A curable composition using an amount of less than 10 ⁻⁸ mol tends to have a slow curing rate and unstable curing. Conversely, a curable composition using an amount exceeding 10 ⁻¹ mol tends to make it difficult to ensure pot life.

  Moreover, a storage stability improving agent can be added to the curable composition containing the components (A) to (C) of the present invention as necessary. The storage stability improver serves to prevent physical properties such as curing and deterioration during storage of the curable composition. The storage stability improver is not particularly limited as long as it is a known stabilizer known as a storage stabilizer of the component (B) of the present invention and achieves the intended purpose. Examples thereof include compounds containing a group unsaturated bond, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds, and organic peroxides. Specifically, 2-benzothiazolyl sulfide, benzothiazole, thiazole, dimethylacetylene dicarboxylate, diethylacetylene dicarboxylate, 2,6-di-t-butyl-4-methylphenol, butylhydroxyanisole, vitamin E, 2- (4-morphodinyldithio) benzothiazole, 3-methyl-1-buten-3-ol, acetylenically unsaturated group-containing organosiloxane, acetylene alcohol, 3-methyl-1-butyl-3-ol Diallyl fumarate, diallyl maleate, diethyl fumarate, diethyl maleate, dimethyl maleate, 2-pentenenitrile, 2,3-dichloropropene, and the like.

  In addition, the curable composition containing the components (A) to (C) of the present invention includes various fillers, antioxidants, ultraviolet absorbers, pigments, surfactants, solvents, and silicon compounds as necessary. You may add suitably.

  Applications of the housing structure of the present invention include mobile phones, mobile personal computers, digital video recorders, digital cameras, and the like.

  Next, although the curable composition of this invention and its crosslinked rubber are demonstrated concretely by an Example, this invention is not limited only to these Examples.

(Production Example 1)
A hydroxyl group-terminated polyoxypropylene polymer having a number average molecular weight of about 20,000 is obtained by polymerizing propylene oxide using a polyoxypropylene diol having a number average molecular weight of 3,000 as an initiator and a composite metal cyanide complex catalyst. Obtained. Subsequently, the end of the hydroxyl group-terminated polyoxypropylene polymer was converted to an allyl group by adding 1.2 times equivalent of a 28% methanol solution of NaOMe and allyl chloride to the hydroxyl group. This reaction product was dissolved in hexane and adsorbed with aluminum silicate, and then the hexane was removed under reduced pressure to give a yellow transparent, polyoxypropylene polymer having an average of two allyl group ends in one molecule (A -1) was obtained. This polymer (A-1) was a pale yellow liquid having a viscosity of 50 Pa · s, and the allyl content determined from the iodine valence was 0.12 mmol / g.

(Production Example 2)
In the presence of a platinum catalyst, 0.5 equivalent of α-methylstyrene of the total amount of hydrosilyl groups is added to methylhydrogen silicone having an average of 10 repeating units represented by (—Si—O—), and added to one molecule. Compound (B-1) having an average of 5 hydrosilyl groups was obtained. The Si—H group content of this compound was 3.8 mmol / g. Here, hydrosilyl group content was computed from the amount of hydrogen which generate | occur | produces by the hydrolysis reaction by the NaOH aqueous solution of the said compound (B-1).

Example 1
100 g of polyoxypropylene polymer having an allyl group terminal (A-1), 2 g of hindered phenol antioxidant (Irganox 245 manufactured by Ciba Specialty Chemicals), 15 g of wet silica (bulk specific gravity 70 g / l), hydrosilyl group Compound (B-1) (2.13 g) having a catalyst, 0.037 g of a platinum vinylsiloxane complex catalyst xylene solution (manufactured by DM Square Japan Co., Ltd., PT-VTSC-3.0X) as a catalyst, preservability improver A curable liquid resin composition was prepared by mixing 0.036 g of acetylene alcohol (Shinfin Chemical Co., Ltd. Surfynol 61).

  The composition thus obtained was liquid, and after defoaming, an aluminum frame mold having a thickness of 2 mm, a width of 25 mm and a length of 100 mm and two mirror-finished press plates were used, and the composition was 125 ° C. A cured sheet with a thickness of 2 mm was obtained by hot press molding for 90 seconds. The obtained sheet was further heat-treated with a 150 ° C. hot air dryer for 1 hour. The resulting cured sheet was conditioned at 23 ° C. and 50 RH% for 24 hours, and then pressure-bonded to a 0.5 mm thick polycarbonate plate (Iupilon NF2000 manufactured by Mitsubishi Engineering Plastics) using a 6 kg roller, and then a digital force gauge The 90 ° peel strength was measured with DS2-50N (manufactured by Imada Co., Ltd.). The results are shown in Table 1. Moreover, three sheets of the obtained cured product sheets were stacked, and the hardness was measured based on the hardness test described in JIS K6253. The results are shown in Table 1.

(Example 2)
100 g of polyoxypropylene polymer having an allyl group terminal (A-1), 2 g of hindered phenol antioxidant (Irganox 245 manufactured by Ciba Specialty Chemicals), 15 g of wet silica (bulk specific gravity 70 g / l), hydrosilyl group Compound (B-1) (5.11 g) having a catalyst, 0.037 g of a platinum vinylsiloxane complex catalyst xylene solution (manufactured by DM Square Japan Co., Ltd., PT-VTSC-3.0X) as a catalyst, preservability improver A curable liquid resin composition was prepared by mixing 0.036 g of acetylene alcohol (Shinfin Chemical Co., Ltd. Surfynol 61).
A cured product sheet was prepared from the above liquid composition by the method described in Example 1, and the 90 ° peel strength and hardness were measured. The results are shown in Table 1.

(Example 3)
The polycarbonate casing 1 shown in FIGS. 1 and 2 is inserted into a mold heated to 125 ° C., and after clamping, the curable liquid resin composition prepared in Example 1 is injected and cured for 60 seconds. By making it react, the housing | casing 1 integrated with packing was created. As a result of observing the appearance, there was no occurrence of flash and it was good. Next, the housing 1 and the housing 2 integrated with the packing were fitted and compressed to a predetermined compression rate, and a waterproof test was performed. For the waterproof test, using an analytical waterproof tester (HPT8701P005 manufactured by Hamron Tech Co., Ltd.), after submerging under a predetermined pressure at 23 ° C. for 30 minutes, visually check whether water has entered the packing or not. Judged. As a result, the waterproofness was good.

Claims (9)

A structure having a housing having a concave groove continuous to the peripheral portion, a housing having a convex portion continuous to the peripheral portion, and an elastic packing integrated in the concave groove of the housing having the concave groove. A casing structure integrated with a packing, characterized in that the formed elastic packing has surface adhesiveness, and the 90 ° peel strength with respect to the casing plate is 3 N / 25 mm or more. The housing structure integrated with packing according to claim 1, wherein the hardness of the elastic packing measured in accordance with JIS K6253 is JIS hardness 40A or less. 3. The packing according to claim 1, wherein a thermosetting liquid resin composition is injected into a cavity formed when a casing having a concave groove at a peripheral edge portion is inserted into a mold and clamped. Manufacturing method of the housing structure integrated with.   4. A housing integrated with a packing according to claim 3, wherein a tab is provided at a position avoiding the fitting portion between the concave groove and the convex portion, and the tab has a pin gate of φ0.8 or less. Manufacturing method of body structure.   The manufacturing method of the housing structure integrated with the packing according to claim 4, wherein a tab is provided at a position where the material is injected from the pin gate and the material joins. The case structure integrated with the packing according to claim 1 or 2, wherein the concave groove formed in the peripheral portion of the case has a width of 1 mm or less and a depth of 1 mm or less.   The taper is formed in the opening part of the concave groove formed in the peripheral part of the housing, and a fixed mold is pressed against the taper part to form the taper part according to any one of claims 3 to 5. A method for manufacturing a housing structure integrated with a packing. The packing integrated housing structure according to claim 1 or 2, wherein the curable liquid resin composition contains the following components (A) to (C).
(A) Organic polymer having a number average molecular weight of 1,000 to 50,000 having at least one alkenyl group on average in one molecule (B) Compound having at least two hydrosilyl groups in one molecule (C ) Hydrosilylation catalyst The polymer (A) according to claim 8 is (a-1) a saturated hydrocarbon polymer, (a-2) a polyoxyalkylene polymer, (a-3) a poly (meth) acrylic polymer. The housing structure integrated with the packing according to claim 8, which is at least one selected from the group consisting of:

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