JP2012031263A - Weatherstrip material - Google Patents

Abstract

[PROBLEMS] To use a material in which the problems of the prior art are solved, excellent in lubricity, abrasion resistance, heat resistance, weather resistance and uniform matting effect, and carbon dioxide is taken into the resin and fixed. By producing weatherstrip materials, it contributes to the reduction of carbon dioxide, which is regarded as a global problem as a global warming gas, and is useful as an environmentally friendly product from the viewpoint of global environmental conservation Offer.
A weatherstrip material for coating and / or impregnating a polymer elastic material to form a surface treatment layer in a sliding contact portion in sliding contact with another component, the isocyanate masked in the molecule A resin composition comprising a self-crosslinking polyhydroxypolyurethane resin containing a group, a diorganopolysiloxane having an average polymerization degree of 5,000 to 10,000 and / or a silicone oil having a viscosity of 100 to 10,000 CS. A weatherstrip material.
[Selection figure] None

Description

  The present invention provides a surface treatment layer for a band-shaped sealing part made of a polymer elastic material for preventing wind and rain from entering through a gap between a body and a part such as a door or window of an automobile or a building. The present invention relates to a resin composition material useful as a forming material. More specifically, when a surface treatment layer is formed in a sliding contact portion that is in sliding contact with other parts of a weather strip made of a polymer elastic body material, the surface treatment layer has particularly good lubricity, wear resistance, and heat resistance. The present invention relates to a useful material that has excellent properties and weather resistance and contributes to environmental conservation.

  Conventionally, as materials for forming weather strips such as glass runs, door weather strips, body side weather strips, inside seals and outside seals of automobiles and buildings, chloroprene rubber, styrene-butadiene rubber, nitrile rubber, EPDM rubber, etc. A polymer elastic material is used. And in order to give these surfaces performances such as lubricity, abrasion resistance, mold release, heat resistance, water resistance and weather resistance, a surface treatment layer may be formed by a method such as coating or impregnation. Has been done.

  As a material for forming such a treatment layer, a thermosetting polyurethane resin added with silicone oil (see Patent Document 1), or a thermosetting polyurethane resin containing an organopolysiloxane (see Patent Document 2). Various coating materials such as urethane prepolymer and silicone oil, hydrophobic silica, and polyisocyanate (see Patent Document 3) have been proposed.

  On the other hand, due to the recent increase in environmental problems, many manufacturers are actively working on environmental measures, and there is a movement to construct products using materials with excellent environmental conservation. For this reason, for example, it is considered that a specific solvent (toluene or the like) is not selected from the organic solvents used in the paint, and a VOC (volatile organic compound) emission amount is minimized by using a water-based resin instead of the organic solvent. Studies to suppress it are also actively conducted (see Patent Document 4). However, it is still insufficient to cope with the current global environmental conservation.

  As materials that can contribute to environmental conservation, as can be seen in Non-Patent Documents 1 and 2, polyhydroxy polyurethane resins using carbon dioxide as a raw material have been known for some time. However, the actual situation is that the application development is not progressing. The reason why the application development does not proceed is that this resin is clearly inferior in characteristics as compared with a polyurethane resin compared with the same type of polymer compound (see Patent Documents 5 and 6).

  In addition, the global warming phenomenon, which is thought to be caused by the ever-increasing carbon dioxide in recent years, has become a global problem, and the reduction of carbon dioxide emissions is an important and prompt response worldwide. This is a desired technical problem. Furthermore, from the viewpoint of the depleted petrochemical resources (oil) problem, the shift to renewable resources such as biomass and methane has become a global trend.

  Against the background as described above, the polyhydroxy polyurethane resin has been reviewed again. In other words, carbon dioxide, the raw material for this resin, is an easily available and sustainable carbon resource, and plastics made from carbon dioxide are effective in solving problems such as global warming and resource depletion. It can be a means.

N. Kihara, T. Endo, J. Org. Chem., 1993, 58, 6198 N. Kihara, T. Endo, J. Polymer Sci., Part A Polmer Chem., 1993, 31 (12), 2765

JP-A-56-4408 JP-A-8-225670 JP-A-8-109349 JP 2008-56772 A US Pat. No. 3,072,613 JP 2000-319504 A

  Under such circumstances, a surface treatment layer provided on a weather strip of an automobile or a building by a method such as coating or impregnation, in particular, has excellent basic characteristics such as lubricity, wear resistance, heat resistance, and weather resistance. It would be very useful if it could be an environmentally friendly product with environmental conservation on a global scale.

  Accordingly, an object of the present invention is to provide a material for forming a surface treatment layer in a sliding contact portion that is in sliding contact with other parts of a polymeric elastic material constituting a weather strip, although it is a material that also contributes to environmental conservation. An object of the present invention is to provide a useful weather strip material in which the formed surface treatment layer is excellent in lubricity, wear resistance, heat resistance and weather resistance.

  The above object is achieved by the present invention described below. That is, the present invention is a weather strip material for coating and / or impregnating a polymer elastic body material to form a surface treatment layer in a sliding contact portion that is in sliding contact with another component, and is masked in the molecule. A resin composition comprising a self-crosslinking polyhydroxypolyurethane resin containing an isocyanate group, a diorganopolysiloxane having an average polymerization degree of 5,000 to 10,000 and / or a silicone oil having a viscosity of 100 to 10,000 CS A material for a weatherstrip is provided.

  The following are mentioned as a preferable form of this invention. The masked isocyanate group is a reaction product of an organic polyisocyanate group and a masking agent. The masked portion is dissociated by heat treatment to form an isocyanate group, which reacts with a hydroxyl group in the structure. The self-crosslinking polyhydroxypolyurethane resin is obtained by modifying a polyhydroxypolyurethane resin derived from the reaction between a 5-membered cyclic carbonate compound and an amine compound with a modifier. The 5-membered cyclic carbonate compound is obtained by reacting an epoxy compound with carbon dioxide; the self-crosslinking polyhydroxypolyurethane resin contains carbon dioxide as a raw material, and carbon dioxide is contained in the resin. 1 to 25% by mass; self-crosslinking polyhydro 1 to 100 parts by mass of diorganopolysiloxane having an average degree of polymerization of 5,000 to 10,000 and / or silicone oil having a viscosity of 100 to 10,000 CS to 100 parts by mass of the polyurethane resin. An additive comprising one or a combination of two or more selected from organic fine powders and inorganic fine powders with respect to 100 parts by mass of the self-crosslinking polyhydroxypolyurethane resin. It is a resin composition blended at a ratio of 150 parts by mass; and further a resin composition comprising a binder resin other than the self-crosslinking polyhydroxy polyurethane resin.

  According to the present invention, a material for forming a surface treatment layer in a sliding contact portion that is in sliding contact with other components of a polymer elastic material that is a base material for a weather strip of an automobile or a building is also environmentally safe. Although the material contributes, provision of a useful material in which the formed surface treatment layer is excellent in lubricity, wear resistance, heat resistance, and weather resistance is achieved. More specifically, in the present invention, a self-crosslinked polyhydroxypolyurethane resin containing an isocyanate group masked in the molecule, a diorganopolysiloxane having an average degree of polymerization of 5,000 to 10,000, and / or a viscosity of Since a composition containing 100 to 10,000 CS silicone oil is used, the formed surface treatment layer has excellent basic characteristics, and of course, carbon dioxide, which is a global warming gas, is used as a raw material. Therefore, it is possible to provide a material that is also useful from the viewpoint of global environmental conservation, and an environment-friendly product using the material.

Next, the present invention will be described in more detail with reference to preferred embodiments.
The weatherstrip material of the present invention is a material for coating and / or impregnating a polymer elastic body material to form a surface treatment layer in a sliding contact portion that is in sliding contact with other components. It contains a cross-linked polyhydroxyurethane resin. The self-crosslinking polyhydroxy polyurethane resin characterizing the present invention has an isocyanate group masked in its structure. The self-crosslinking polyhydroxypolyurethane resin can be obtained, for example, by reacting with a hydroxyl group in the polyhydroxypolyurethane resin using a modifier having at least one free isocyanate group and a masked isocyanate group. it can. Furthermore, the polyhydroxy polyurethane resin is preferably a resin derived from a reaction between a 5-membered cyclic carbonate compound and an amine compound. Since the 5-membered cyclic carbonate compound is obtained by reacting an epoxy compound with carbon dioxide, it becomes a material that contributes to environmental conservation. Below, each component is demonstrated.

[Self-crosslinking type polyhydroxy polyurethane resin]
(Modifier)
The components of the modifier used in the production of the self-crosslinking polyhydroxypolyurethane resin used in the present invention will be described. As the modifier, a reaction product of an organic polyisocyanate compound and a masking agent is used. The organic polyisocyanate compound used at this time is an organic compound having at least two isocyanate groups in an aliphatic or aromatic compound, and has been widely used as a raw material for synthesizing polyurethane resins. Any of these known organic polyisocyanate compounds are useful in the present invention. Particularly preferable organic polyisocyanate compounds are as follows.

  For example, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 4,4′- Examples include dicyclohexylmethane diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, and xylylene diisocyanate. Furthermore, adducts of these organic polyisocyanate compounds and other compounds, for example, those having the following structural formula can be suitably used, but are not limited thereto.

  The modifying agent used in the present invention is a reaction product of the organic polyisocyanate compound and the masking agent described above, and the following can be used as the masking agent. There are alcohol-based, phenol-based, active methylene-based, acid amide-based, imidazole-based, urea-based, oxime-based and pyridine-based compounds, and these may be used alone or in combination. As specific masking agents, any of the compounds listed below can be used.

  Examples of alcohols include methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, and cyclohexanol. Examples of the phenol type include phenol, cresol, ethylphenol, nonylphenol and the like. Examples of the active methylene type include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone. Examples of acid amides include acetanilide, acetic acid amide, caprolactam, and γ-butyrolactam. Examples of the imidazole series include imidazole and 2-methylimidazole. Examples of the urea system include urea, thiourea, and ethylene urea. Examples of the oxime type include formamide oxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime. Examples of the pyridine series include 2-hydroxypyridine and 2-hydroxyquinoline.

<Method of synthesizing denaturant>
A modification having at least one free isocyanate group and other having a masked isocyanate group used in the present invention by reacting the organic polyisocyanate compound listed above with the masking agent listed above. Synthesize the agent. Although the synthesis method is not particularly limited, the masking agent as described above and the organic polyisocyanate compound are functional groups in which one or more isocyanate groups are excessive in one molecule, in the presence or absence of an organic solvent and a catalyst. It can be easily obtained by reacting at a temperature of 0 to 150 ° C., preferably 20 to 80 ° C. for 30 minutes to 3 hours.

(Polyhydroxy polyurethane resin)
The self-crosslinking polyhydroxypolyurethane resin modified with the specific modifier as described above used in the present invention is derived from, for example, a polyhydroxypolyurethane resin obtained by a reaction between a 5-membered cyclic carbonate compound and an amine compound. The Below, each component used in this case is demonstrated.

<5-membered cyclic carbonate compound>
The 5-membered cyclic carbonate compound used above can be produced by reacting an epoxy compound and carbon dioxide, as shown by the following [Formula-A]. More specifically, the epoxy compound is carbon dioxide in the presence or absence of an organic solvent and in the presence of a catalyst at a temperature of 40 ° C. to 150 ° C. for 10-20 hours at normal pressure or slightly elevated pressure. It is obtained by reacting with.

Examples of the epoxy compound that can be used above include the following compounds.

  The epoxy compounds listed above are preferable compounds that can be used to obtain the polyhydroxy polyurethane resin constituting the present invention, and the present invention is not limited to these exemplified compounds. Accordingly, not only the compounds exemplified above, but also any other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention.

<Catalyst and reaction>
As the catalyst used in the reaction between the epoxy compound as described above and carbon dioxide, a base catalyst and a Lewis acid catalyst described below can be used.
Base catalysts include tertiary amines such as triethylamine and tributylamine, cyclic amines such as diazabicycloundecene, diazabicyclooctane and pyridine, alkali metal salts such as lithium chloride, lithium bromide, lithium fluoride and sodium chloride , Alkaline earth metal salts such as calcium chloride, quaternary ammonium salts such as tetrabutylammonium chloride, tetraethylammonium bromide, benzyltrimethylammonium chloride, carbonates such as potassium carbonate and sodium carbonate, zinc acetate, lead acetate, copper acetate And metal acetates such as iron acetate, metal oxides such as calcium oxide, magnesium oxide and zinc oxide, and phosphonium salts such as tetrabutylphosphonium chloride.

  Examples of the Lewis acid catalyst include tin compounds such as tetrabutyltin, dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin octoate.

  The amount of the catalyst may be about 0.1 to 100 parts by mass, preferably 0.3 to 20 parts by mass, per 50 parts by mass of the epoxy compound. When the amount used is less than 0.1 parts by mass, the effect as a catalyst is small, and when it exceeds 100 parts by mass, various performances of the final resin are lowered. However, if the residual catalyst causes a serious performance degradation, it may be removed by washing with pure water.

  Examples of the organic solvent that can be used in the reaction of the epoxy compound and carbon dioxide include dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, and tetrahydrofuran. These organic solvents and other poor solvents such as methyl ethyl ketone, xylene, toluene, tetrahydrofuran, diethyl ether, and cyclohexanone may be used in a mixed system.

  As shown by the following [Formula-B], the polyhydroxypolyurethane resin used in the present invention is obtained by combining a 5-membered cyclic carbonate compound obtained as described above and an amine compound in the presence of an organic solvent. It can obtain by making it react at the temperature of 150 degreeC-150 degreeC.

<Amine compound>
As the amine compound used in the present invention, any of those conventionally used in the production of polyurethane resins can be used and is not particularly limited, but diamines listed below are preferred. For example, aliphatic diamines such as methylene diamine, ethylene diamine, trimethylene diamine, 1,3-diaminopropane, hexamethylene diamine and octamethylene diamine; phenylene diamine, 3,3′-dichloro-4,4′-diaminodiphenyl methane, 4 , 4′-methylenebis (phenylamine), 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, metaxylylenediamine, paraxylylenediamine, and the like; 1,4-cyclohexanediamine, 4 , 4'-diaminocyclohexylmethane, 1,4'-diaminomethylcyclohexane, isophoronediamine and other alicyclic diamines; monoethanoldiamine, ethylaminoethanolamine and hydroxyethylaminopropylamine Nol diamine is mentioned.

  The amine compounds listed above are preferable compounds used in the present invention, and the present invention is not limited to these exemplified compounds. Accordingly, not only the above-exemplified compounds but also any other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention.

<Physical properties>
The polyhydroxy polyurethane resin constituting the present invention preferably has a number average molecular weight (standard polystyrene conversion value measured by GPC) of about 2,000 to 100,000, more preferably 5,000 to 70,000. About 000. Furthermore, the hydroxyl value of the polyhydroxy polyurethane resin is preferably 20 to 300 mgKOH / g. When the hydroxyl group content is less than the above range, the effect of reducing carbon dioxide is insufficient, while when it exceeds the above range, various physical properties as a polymer compound are insufficient.

(Modification to self-crosslinking polyhydroxy polyurethane resin)
The self-crosslinking type polyhydroxypolyurethane resin constituting the present invention is obtained by the polyhydroxypolyurethane resin and the modifier obtained as described above, respectively. Specifically, a polyhydroxy polyurethane resin modified to be a self-crosslinking type by reacting a hydroxyl group in the polyhydroxy polyurethane resin with at least one free isocyanate group in the modifier is used.

The modification rate of the self-crosslinking polyhydroxypolyurethane resin constituting the present invention with a modifier is preferably 2 to 60%, and more preferably 5 to 40%. Depending on the ratio of the modification rate, the performance such as wear resistance, chemical resistance and heat resistance after heat treatment can be controlled to some extent. If the modification rate is less than 2%, the properties such as heat resistance and chemical resistance required for weather strips obtained by sufficient cross-linking may not be sufficiently obtained, which is not preferable. On the other hand, when the modification rate exceeds 60%, it is preferable that the over-crosslinking impairs the folding whitening property suitable as a weather strip and increases the possibility that the dissociated isocyanate group remains without reacting in the resin. Absent. In addition, the modification | denaturation rate by the modifier | denaturant of the hydroxyl group of a polyhydroxy polyurethane resin is computed as follows.
Modification rate (%) = {1− (hydroxyl group of resin after modification ÷ hydroxyl group of resin before modification)} × 100

  The reaction between the modifier and the polyhydroxypolyurethane resin is facilitated by reacting at a temperature of 0 to 150 ° C., preferably 20 to 80 ° C. for 30 minutes to 3 hours in the presence or absence of an organic solvent and a catalyst. Obtainable. However, during the reaction, attention should be paid to the fact that the reaction is carried out at a temperature lower than the dissociation temperature of the masking agent, so that the structure of the modified self-crosslinked polyhydroxy polyurethane resin has a masked isocyanate group.

[Diorganopolysiloxane]
The diorganopolysiloxane blended in the above-described self-crosslinking polyhydroxypolyurethane resin constituting the material of the present invention has an average polymerization degree of 5,000 to 10,000. Such is a straight-chain non-fluid rubbery silicone that is readily available from the market. Since the organopolysiloxane (silicone) having an average polymerization degree in such a range has a high viscosity, in the film formed by the weatherstrip material of the present invention containing such an organopolysiloxane (silicone), It is considered that the orientation (bleed) proceeds slowly.

  For this reason, the inventors of the present invention can form a surface treatment layer using the weather strip material of the present invention at the sliding contact portion that is in sliding contact with the other parts of the polymer elastic body material, which is a base material. It is inferred that it has become possible to maintain the performance over the entire period. Examples of commercially available products include high viscosity series of silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., and any of these can be used. Specifically, KF96H-6,000 cs, KF96H-10,000 cs, KF96H-12,500 cs, KF96H-30,000 cs, KF96H-50,000 cs, KF96H-60,000 cs, KF96H-10,000 cs, KF96H-30 10,000 cs, KF96H-500,000 cs, and KF96H-1 million cs (the above are trade names). Among these, KF96H-6,000 cs to KF96H-50,000 cs, more preferably KF96H-10,000 cs to KF96H-30,000 cs may be used.

[Silicone oil]
In the present invention, instead of or in addition to the diorganopolysiloxane (silicone), a silicone oil having a low kinematic viscosity in the range of 100 to 10,000 CS is blended in the self-crosslinking polyhydroxy polyurethane resin. When a small amount of such a low-viscosity silicone oil is added in addition to the high-viscosity silicone, the orientation of the silicone (bleed) on the coating surface can be controlled, so that the range of selection of the silicone material can be expanded. The amount of the low viscosity silicone oil used relative to the high viscosity silicone is preferably about 100: 3 to 20. The silicone oil may or may not have an active hydrogen group that reacts with a polyisocyanate that is a crosslinking agent used in the synthesis of the polyurethane resin used in the present invention. In the present invention, CS means centistokes [cSt] that is 1 / 100th of Stokes.

  The above-mentioned diorganopolysiloxane and / or silicone oil constituting the resin composition which is a weatherstrip material of the present invention is 1 to 100 parts by weight, preferably 100 parts by weight, preferably 100 parts by weight of polyhydroxypolyurethane resin. It mixes in 3-70 mass parts, More preferably, in the range of 10-30 mass parts. If the blending amount is less than 1 part by mass, the added effect is too small. On the other hand, if the blending amount exceeds 100 parts by mass, the coating tends to be weak, which is not preferable.

[Other ingredients]
In addition, the resin composition, which is a material for a weather strip of the present invention, may be one kind of organic fine powder and / or inorganic fine powder in order to improve the matte surface of the formed treatment layer and to improve wear and lubricity. It is preferable to use a combination of two or more. The organic fine powder is not particularly limited, and examples thereof include acrylic resin particles, styrene resin particles, styrene-acrylic resin particles, phenol resin particles, melamine resin particles, acrylic-polyurethane resin particles, polyurethane resin particles, and polyester. Resin particles, nylon resin particles, silicone resin particles, polyethylene resin particles, and the like can be used. These powders preferably have an average particle size in the range of 1 to 50 μm. Moreover, since the surface property improvement and matting property of the formed coating film are particularly excellent, the shape of the particles is preferably spherical or substantially spherical.

  Examples of the inorganic fine powder include talc, mica, calcium carbonate, barium sulfate, magnesium carbonate, clay, alumina, silica, carbon fiber, glass fiber, metal fiber, carbon black, titanium oxide, molybdenum, and magnesium hydroxide. Bentonite, graphite and the like can be used. The average particle size of these powders is 10 μm or less in accordance with the object of the present invention, but a powder having a particle size as small as possible is more preferable.

  The amount of the matting agent as mentioned above is 1 to 150 parts by mass, preferably 3 to 60 parts by mass with respect to 100 parts by mass of the self-crosslinking type polyhydroxy polyurethane resin. If the amount is less than 1 part by mass, the effect of addition cannot be sufficiently obtained. On the other hand, if it exceeds 150 parts by mass, the mechanical properties of the coating film tend to be greatly reduced, which is not preferable.

  The resin composition comprising as a main component the self-crosslinking polyhydroxypolyurethane resin constituting the present invention is basically an organic solvent solution or water dispersion (solution) comprising the self-crosslinking polyhydroxypolyurethane resin described above. It is. Preferable organic solvents used when the resin composition is an organic solvent solution include dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone and the like. Moreover, it is preferable that the resin density | concentration in an organic solvent is 3-60 mass%. When the resin concentration is less than 3% by mass, the film formability is inferior and the film thickness is insufficient, resulting in insufficient strength. On the other hand, if the resin concentration exceeds 60% by mass, the formation of the film after drying may be incomplete, and problems such as residual organic solvent in the film may occur.

  When the resin composition mainly composed of the self-crosslinking type polyhydroxy polyurethane resin constituting the present invention is used as an aqueous dispersion (solution), it is preferably prepared as follows. First, a carboxyl group is introduced into the resin by semi-esterifying or semi-amidating a hydroxyl group or NH group in the self-crosslinking polyhydroxy polyurethane resin with an acid anhydride. Thereafter, the carboxyl group is preferably neutralized with ammonia, an organic amine compound, an inorganic base or the like to form a carboxylate and used as a self-emulsifying aqueous dispersion. Examples of the acid anhydride used at this time include phthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, and the like. Moreover, as an organic amine compound, monoethanolamine, diethanolamine, triethanolamine, diethylethanolamine, aminoethylethanolamine, etc. can be used. The self-crosslinking polyhydroxypolyurethane resin may be an aqueous dispersion emulsified in water with a surfactant according to a conventional method.

  Further, in the resin composition comprising the self-crosslinking polyhydroxypolyurethane resin as a main component constituting the present invention, in the case of forming a surface treatment layer by applying to a polymer elastic body which is a base material of a weather strip, In order to improve the adhesion and the film formability of the coating film, various conventionally known binder resins can be further mixed and used. In this case, as the binder resin to be used, those capable of chemically reacting with isocyanate groups generated by dissociation of the masking agent in the self-crosslinking type polyhydroxy polyurethane resin are preferable, but those having no reactivity are also acceptable. Can be used.

  As these binder resins, binder resins conventionally used for surface treatment of weatherstrips can be used, and are not particularly limited. For example, acrylic resin, polyurethane resin, polyester resin, polybutadiene resin, silicone resin, melamine resin, phenol resin, polyvinyl chloride resin, cellulose resin, alkyd resin, modified cellulose resin, fluorine resin, polyvinyl butyral resin, epoxy resin, polyamide resin Etc. can be used. When these binder resins are used in combination, the amount used may be determined in consideration of the functionality, but can be used in the range of 5 to 90% by mass. Even when 90% by mass of a binder resin other than the self-crosslinking type polyhydroxypolyurethane resin is used, what can be said to be a sufficiently environmentally friendly product is obtained. However, in order to make the product an environmentally friendly product that also contributes to environmental conservation, a self-crosslinking polyhydroxy polyurethane resin using carbon dioxide as a raw material and fixing carbon dioxide in its structure is used. It is preferable that the product is used in large quantities.

  In addition, the resin composition comprising the self-crosslinking polyhydroxy polyurethane resin constituting the present invention and additives such as diorganopolysiloxane and silicone oil may include a coating surface conditioner, a fluidity conditioner, Various paint additives such as ultraviolet absorbers, dispersants and anti-settling agents may be added as appropriate.

  A weather strip having a surface treatment layer with excellent functionality by using the weather strip material of the present invention comprising a resin composition in which diorganopolysiloxane, silicone oil or the like is blended with the self-crosslinking polyhydroxy polyurethane resin described above. Enables the formation of Specifically, by coating and / or impregnating the material of the present invention with a polymer elastic body, a surface treatment layer having excellent functionality can be easily formed on the sliding contact portion of the base material that is in sliding contact with other components. Can do. For example, the weatherstrip material of the present invention is applied to the polymer elastic body by a known application method such as brush coating, spraying, roll coating, gravure, or dipping so that the thickness after drying is about 10 to 100 μm. After drying, the surface treatment layer can be formed by heat treatment at a temperature of about 50 to 170 ° C. That is, when the heat treatment is performed, the masking agent for the masked isocyanate group in the molecule of the self-crosslinking polyhydroxypolyurethane resin is dissociated to form an isocyanate group, and the isocyanate group is contained in the self-crosslinking polyhydroxypolyurethane resin. By reacting with the free hydroxyl group, a self-crosslinking film is formed. As a result, a weatherstrip product having a surface-treated layer with a film formed on a polymer elastic body for weatherstrip and having excellent functionality can be obtained.

  As described above, the weatherstrip material of the present invention contains a self-crosslinking polyhydroxypolyurethane resin and a specific diorganopolysiloxane and / or a specific silicone oil. By using and molding the surface treatment layer at a desired position of the polymer elastic body, a weather strip excellent in lubricity, abrasion resistance, heat resistance, weather resistance and uniform matting effect can be obtained. In addition, the self-crosslinking polyhydroxypolyurethane resin used in the present invention is useful from the viewpoint of reducing greenhouse gases because carbon dioxide can be incorporated into the resin during synthesis. It is possible to provide a weather strip that could not be used for environmental conservation.

  Next, although a manufacture example, a polymerization example, an Example, and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these Examples. In the following examples, “part” and “%” are based on mass unless otherwise specified.

[Production Example 1 (Production of modifier)]
While stirring 100 parts of trimethylolpropane and hexamethylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane, Coronate HL, NCO = 12.9%, solid content 75%) and 24.5 parts of ethyl acetate at 100 ° C. , 25.5 parts of ε-caprolactam was added and allowed to react for 5 hours. According to the infrared absorption spectrum of the obtained modifier (Horiba FT-720), absorption due to free isocyanate groups remains at 2270 cm ⁻¹ , and when this free isocyanate group is determined, a theoretical value is obtained at a solid content of 50%. Was 2.1%, while the measured value was 1.8%.

The main structure of the above modifier is assumed to be the following formula.

[Production Example 2 (Production of modifier)]
Addition of hexamethylene diisocyanate and water adduct (Asahi Kasei Co., Ltd., Duranate 24A-100, NCO = 23.0%) 100 parts, stirring ethyl acetate at 80 ° C., 32 parts of methyl ethyl ketoxime was added and reacted for 5 hours. I let you. According to the infrared absorption spectrum of the obtained modifier, absorption due to free isocyanate groups remains at 2270 cm ⁻¹ , and when this free isocyanate group is determined, the theoretical value is 2.9% at a solid content of 50%. On the other hand, the measured value was 2.6%.

The main structure of the above modifier is assumed to be the following formula.

[Production Example 3 (Production of modifier)]
While stirring 100 parts of trimethylolpropane and tolylene diisocyanate trimer adduct (manufactured by Nippon Polyurethane Co., Ltd., Coronate L, NCO = 12.5%, solid content 75%) and 67.3 parts of ethyl acetate at 80 ° C. Then, 17.3 parts of methyl ethyl ketoxime was added and reacted for 5 hours. According to the infrared absorption spectrum of the obtained modifier, absorption due to free isocyanate groups remains at 2270 cm ⁻¹ , and when this free isocyanate group is quantified, the theoretical value is 2.3% at a solid content of 50%. On the other hand, the measured value was 2.0%.

The main structure of the above modifier is assumed to be the following formula.

[Production Example 4 (Production of 5-membered cyclic carbonate compound)]
In a reaction vessel equipped with a stirrer, a thermometer, a gas introduction pipe and a reflux condenser, a divalent epoxy compound represented by the following formula A (Japan Epoxy Resin Co., Ltd., Epicoat 828; epoxy equivalent 187 g / mol) 100 Part, 100 parts of N-methylpyrrolidone and 1.5 parts of sodium iodide were added and dissolved uniformly. Thereafter, the mixture was heated and stirred at 80 ° C. for 30 hours while bubbling carbon dioxide at a rate of 0.5 liter / min. After completion of the reaction, the obtained solution was gradually added to 300 parts of n-hexane with high-speed stirring at 300 rpm, and the resulting powdery product was filtered with a filter and further washed with methanol, and N-methylpyrrolidone. And sodium iodide was removed. The powder was dried in a drier to obtain 118 parts (yield 95%) of a white powder 5-membered cyclic carbonate compound (1-A).

The infrared absorption spectrum of the product obtained above shows that the peak derived from the epoxy group near 910 cm ⁻¹ almost disappears in the product, and the carbonyl group of the cyclic carbonate group that does not exist in the raw material exists near 1800 cm ⁻¹ . Absorption was confirmed. Moreover, the number average molecular weight of the product was 414 (polystyrene conversion, Tosoh; GPC-8220). In the obtained 5-membered cyclic carbonate compound (1-A), 19% of carbon dioxide is immobilized.

[Production Example 5 (Production of 5-membered cyclic carbonate compound)]
Instead of the divalent epoxy compound represented by the formula A used in Production Example 4, a divalent epoxy compound represented by the following formula B (manufactured by Toto Kasei Co., Ltd., YDF-170; epoxy equivalent 172 g / mol) was used. The reaction was conducted in the same manner as in Production Example 4 to obtain 121 parts (yield 96%) of a white powder 5-membered cyclic carbonate compound (1-B). The product was confirmed by infrared absorption spectrum, GPC and NMR. In the obtained 5-membered cyclic carbonate compound (1-B), 20.3% of carbon dioxide is immobilized.

[Polymerization Example 1 (Production of Self-Crosslinking Polyhydroxy Polyurethane Resin)]
A reaction vessel equipped with a stirrer, a thermometer, a gas introduction tube and a reflux condenser was replaced with nitrogen, and 100 parts of the 5-membered cyclic carbonate compound (1-A) obtained in Production Example 4 was added to the reaction vessel. N-methylpyrrolidone was added to 35% and dissolved uniformly. Next, 27.1 parts of hexamethylenediamine was added, and the mixture was stirred at a temperature of 90 ° C. for 10 hours, and reacted until no hexamethylenediamine could be confirmed. Next, 20 parts of the modifier (solid content 50%) obtained in Production Example 1 was added and reacted at 90 ° C. for 3 hours. After confirming that the absorption of the isocyanate group by the infrared absorption spectrum disappeared, a self-crosslinking polyhydroxy polyurethane resin solution was obtained.

[Polymerization Examples 2 to 4 (Production of Self-Crosslinking Polyhydroxy Polyurethane Resin)]
Hereinafter, in the same manner as in Polymerization Example 1, the modifiers obtained in 5-membered cyclic carbonate compound (1-A) or (1-B), polyamine compound, Production Example 2 or Production Example 3 are listed in Table 1. In combination, self-crosslinked polyhydroxypolyurethane resin solutions of Polymerization Examples 2 to 4 were obtained.

[Comparative Polymerization Example 1 (Production of Polyhydroxy Polyurethane Resin)]
In Polymerization Example 1, an unmodified polyhydroxy polyurethane resin solution was obtained in the same manner as in Polymerization Example 1 except that no modifier was used.

[Comparative polymerization example 2 (polyester urethane resin)]
A reaction vessel equipped with a stirrer, a thermometer, a gas introduction tube and a reflux condenser was replaced with nitrogen, 150 parts of polybutylene adipate having an average molecular weight of about 2,000, and 15 parts of 1,4-butanediol were 200 parts. Into a mixed organic solvent consisting of 50 parts of dimethylformamide and slowly stirring at 60 ° C., 62 parts of water-added MDI dissolved in 171 parts of dimethylformamide were gradually added dropwise. After completion, the reaction was carried out at 80 ° C. for 6 hours. This solution had a viscosity of 3.2 MPa · s (25 ° C.) at a solid content of 35%. The film obtained from this solution had a breaking strength of 45 MPa, a breaking elongation of 480%, and a thermal softening temperature of 110 ° C.

[Comparative polymerization example 3 (polycarbonate polyurethane resin)]
In the same manner as in Comparative Polymerization Example 1, 150 parts of polycarbonate diol (Ube Industries, Ltd.) having an average molecular weight of about 2,000, 15 parts of 1,4-butanediol, 200 parts of methyl ethyl ketone and 50 parts of Dissolve in a mixed organic solvent consisting of dimethylformamide, slowly add dropwise 62 parts of water-added MDI in 171 parts of dimethylformamide while stirring well at 60 ° C. Reacted for hours. This solution had a viscosity of 1.6 MPa · s (25 ° C.) at a solid content of 35%. The film obtained from this solution had a breaking strength of 21 MPa, a breaking elongation of 250%, and a thermal softening temperature of 135 ° C.

[Examples 1-8, Comparative Examples 1-6]
Using the resin solutions (paints) of Polymerization Examples 1 to 4 and Comparative Polymerization Examples 1 to 3, blended paints listed in Tables 2 and 3 were prepared. Then, it was coated on an EPDM rubber sheet using an air spray gun and dried at 140 ° C. for 10 minutes to form a 20 μm film on the sheet. The EPDM rubber sheet having the coating surface obtained as described above was used as a measurement sample for evaluating the surface treatment layer (coating surface) formed by each weather strip material.

[Evaluation]
For the weatherstrip material (paint) obtained above and each measurement sample described above, the static friction coefficient, dynamic friction coefficient, contact angle, adhesion, wear durability, weather resistance, etc. were measured by the following methods, respectively. And the material of the comparative example was evaluated. The evaluation results are summarized in Tables 2 and 3.

(Static friction coefficient, dynamic friction coefficient)
The surface friction tester (manufactured by Shinto Kagaku Co., Ltd.) evaluated the coefficient of static friction and the coefficient of dynamic friction of each weather strip material (paint) with the glass member.

(Contact angle)
The contact angle of water in the film part of the measurement sample obtained above was measured with a contact angle meter (manufactured by Kyowa Interface Chemical Co., Ltd.), and the contact angle of water on the coating surface formed using each weather strip material and did.

(Adhesiveness)
The film portion of the measurement sample obtained above was subjected to a peel test by a cross cellophane tape peel test, and the adhesion of the paint film surface made of each weather strip material was evaluated according to the following criteria.
○: Good (no peeling part on the coated surface)
×: Defect (there is a peeled part on the coated surface)

(Abrasion durability)
The surface of the measurement sample obtained above is brought into contact with a glass plate to which a load of 9.8 N is applied, and the number of reciprocating motions until the coating film tears by reciprocating the glass plate Measured with a sex tester (manufactured by Shinto Kagaku). And the abrasion durability of the coating-film surface which consists of each weatherstrip material was evaluated by the obtained reciprocation frequency | count.

(Weather resistance test)
Using a sunshine carbon arc weathering tester (Suga tester), the film part of the measurement sample obtained above was irradiated for 200 hours at a panel temperature of 83 ° C., and the state of the film surface was visually observed. The weather resistance of the coating film surface made of the strip material was evaluated according to the following criteria.
3: No change in surface condition 2: Some change in surface condition 1: Large change and whitening phenomenon

(Environmental compatibility)
It evaluated by (circle) x by the presence or absence of the fixation of the carbon dioxide in each weatherstrip material (paint).

  According to the present invention, a weatherstrip material is masked to be dissociated by heat in its structure by molding with a resin composition comprising a self-crosslinking polyhydroxypolyurethane resin and an additive. Since isocyanate groups and hydroxyl groups in the resin react to form a cross-linked resin, a weatherstrip material with excellent lubricity, abrasion resistance, heat resistance, weather resistance, and uniform matting effect can be obtained. Obtainable.

  The self-crosslinking polyhydroxypolyurethane resin, which is the main component of the resin composition used in the present invention, is a useful material that contributes to solving problems such as global warming and resource depletion by incorporating carbon dioxide into the resin and fixing it. Therefore, the material for weatherstrip obtained by using this can also provide products for environmental protection that cannot be achieved by conventional products.

Claims (8)

  A weatherstrip material for coating and / or impregnating a polymer elastic body material to form a surface treatment layer at a sliding contact portion that is in sliding contact with another component, and containing an isocyanate group masked in the molecule A resin composition comprising a self-crosslinking polyhydroxypolyurethane resin, a diorganopolysiloxane having an average polymerization degree of 5,000 to 10,000, and / or a silicone oil having a viscosity of 100 to 10,000 CS. Weather strip material.   The masked isocyanate group is a reaction product of an organic polyisocyanate group and a masking agent, and the masked portion is dissociated by heat treatment to form an isocyanate group, which reacts with a hydroxyl group in the structure. The weatherstrip material according to claim 1, which self-crosslinks.   The weather according to claim 1 or 2, wherein the self-crosslinking polyhydroxypolyurethane resin is obtained by modifying a polyhydroxypolyurethane resin derived from a reaction between a 5-membered cyclic carbonate compound and an amine compound with a modifier. Strip material.   The weather strip material according to claim 3, wherein the five-membered cyclic carbonate compound is obtained by reacting an epoxy compound with carbon dioxide.   The weatherstrip material according to claim 1, wherein the self-crosslinking polyhydroxypolyurethane resin contains carbon dioxide as a raw material and contains 1 to 25% by mass of carbon dioxide in the resin.   The resin composition comprises 1 diorganopolysiloxane having an average degree of polymerization of 5,000 to 10,000 and / or silicone oil having a viscosity of 100 to 10,000 CS with respect to 100 parts by mass of the self-crosslinking polyhydroxypolyurethane resin. The material for weather strips according to any one of claims 1 to 5, which is blended at a ratio of -100 parts by mass.   1 to 150 parts by mass of an additive comprising one or a combination of two or more selected from organic fine powder and inorganic fine powder with respect to 100 parts by mass of the self-crosslinking polyhydroxypolyurethane resin. The material for weather strips according to any one of claims 1 to 6, which is blended at a ratio of   The weatherstrip material according to any one of claims 1 to 7, wherein the resin composition further comprises a binder resin other than the self-crosslinking polyhydroxypolyurethane resin.