JP4904928B2 - Curable resin composition for casting and tire pressure sensor - Google Patents

Description

  The present invention relates to a curable resin composition for casting and a tire pressure sensor.

In recent years, in order to ensure the safety of automobiles, systems for monitoring tire air pressure have been developed. In the tire pressure monitoring system, there is a method for directly measuring tire air pressure (air pressure direct measurement method). In general, the direct air pressure measurement method connects a pneumatic sensor, one receiving antenna on the vehicle body side, a receiver, a warning light arranged in a combination meter, and a receiving antenna and receiver. Consists of a coaxial cable and a coaxial cable connecting the receiver and the combination meter. The air pressure sensor usually includes a base having a pressure sensor and a radio wave transmitter, and a battery.
In the direct air pressure measurement method, information on the air pressure in the tire measured by the pressure sensor of the air pressure sensor is transmitted to the vehicle body side by a radio wave transmitter and received by a receiver via a receiving antenna. The receiver determines whether the received air pressure value is normal or abnormal, and if it is abnormal, turns on the warning light located in the combination meter to inform the driver of the tire air pressure abnormality and check it. Prompt.

There are two types of air pressure sensors: a type in which an air pressure sensor is fixed with a nut to an air injection valve attached to the tire wheel, and a type in which an air pressure sensor is fixed to an rim of the tire wheel with an adhesive or welding.
An air pressure sensor of the type that is fixed to an air injection valve with a nut is usually composed of a base containing a pressure sensor and a radio wave transmitter, a battery, a valve, a case, and a potting material. In this type of air pressure sensor, a valve and a case are integrated. A base and a battery are accommodated in the case, and a potting material is poured into the case and hardened to fix the base and the battery to the case.
A pneumatic sensor of a type that is fixed to a tire wheel rim by an adhesive or welding is usually composed of a base with a built-in pressure sensor and radio wave transmitter, a battery, a case, and a potting material. In this type of air pressure sensor, a base and a battery are housed in a case, and a potting material is injected into the case to be cured, thereby fixing the base and the battery to the case. This type of air pressure sensor is lighter than the type that is fixed to the air injection valve with a nut.
When such a pneumatic sensor is attached to a tire, it is necessary to attach a weight for correcting the balance of the tire somewhere on the rim.
Therefore, if the air pressure sensor is heavy, a heavy weight must be attached, and as a result, the running performance is often adversely affected. For this reason, the air pressure sensor needs to be light.

Conventionally, as a potting material used for an air pressure sensor, a silicone-based or epoxy-based material for the purpose of sealing an electronic / electrical material has been used. However, these potting materials have a problem that their specific gravity is large and heavy.
In order to provide a low specific gravity polyorganosiloxane composition having excellent mechanical properties of a cured product, for example, Patent Document 1 discloses “(A) a silicon functional group in a molecule. Two or more silicon functional polyorganosiloxanes, (B) curing catalyst, (C) purity 96% or more, (C) 50% breaking pressure due to hydrostatic pressure, 100kgf / cm ² or more borosilicate glass hollow filling A low specific gravity room temperature curable polyorganosiloxane composition characterized by containing an agent. " Patent Document 1 describes that the component (C) is a surface hydroxyl group treated with an organosilicon compound.

Patent Document 2 states that “an epoxy resin composition for semiconductor encapsulation containing the following components (A) to (D) as essential components, wherein the component (A) and the component (B) are the above (A ) The epoxy equivalent X of the epoxy resin as the component and the total amount (X + Y) of the hydroxyl equivalent Y of the phenol resin as the component (B) are set to be 350 or more. Epoxy resin composition.
(A) Epoxy resin.
(B) Phenolic resin.
(C) A curing accelerator.
(D) A hollow inorganic filler having an average particle diameter of 4 to 100 μm and an average shell thickness of 1.5 μm or more. Is described. It also describes that the particle surface of the hollow inorganic filler is previously coated with a silane coupling agent.

JP 2000-0117175 A JP 2001-354754 A

However, the present inventor, when the room temperature curable polyorganosiloxane composition described in Patent Document 1 is allowed to stand, has a hollow borosilicate glass in the room temperature curable polyorganosiloxane composition. It has been found that the filler is separated immediately. About such separation, the inventor inferred that there is a large difference between the specific gravity of the borosilicate glass hollow filler and the specific gravity of the silicon-functional polyorganosiloxane. Moreover, it discovered that the room temperature curable polyorganosiloxane composition described in patent document 1 was easy to gelatinize.
Moreover, about the epoxy resin composition for semiconductor sealing described in patent document 2, the inventor discovered that the viscosity is high and fluidity | liquidity is bad, and it is easy to gelatinize.

  Accordingly, an object of the present invention is to provide a curable resin composition for casting that is unlikely to cause separation and gelation of a glass balloon, has a low viscosity, and can be a lightweight cured product.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventor is a composition having a curable resin, a curing agent and / or a curing catalyst, and a specific glass balloon, and the specific glass balloon is cured with the curable resin. It was found that a specific amount contained in the total amount with the agent and / or the curing catalyst is less likely to cause separation and gelation of the glass balloon, has a low viscosity, and can be a light cured product. It came to complete.

That is, the present invention provides the following (1) to (6).
(1) A curable resin composition for casting having a main agent containing a curable resin and an additive containing a curing agent and / or a curing catalyst,
At least one of the main agent and the additive includes a chain saturated hydrocarbon group-containing glass balloon that can be obtained by reacting a glass balloon and a silicon atom-containing compound represented by the following formula (1):
The amount of the chain saturated hydrocarbon group-containing glass balloon is 1 to 30 parts by mass with respect to a total of 100 parts by mass of the curable resin and the curing agent and / or curing catalyst. object.
(R ¹ O) _m -Si-R ² _4-m (1)
(In the formula, each R ¹ independently represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and each R ² independently represents a monovalent trivalent atom having 3 or more carbon atoms which may contain a hetero atom. Represents a chain saturated hydrocarbon group, and m is an integer of 1 to 3.)
(2) The curable resin composition for casting according to the above (1), wherein the chain saturated hydrocarbon group-containing glass balloon is contained in both the main agent and the additive.
(3) The curable resin composition for casting according to the above (1) or (2), wherein the hardness after curing is 60 or more in JIS A hardness.
(4) A case that can be obtained by injecting and curing the curable resin composition for casting according to any one of (1) to (3) above in a case in which a pressure sensor and a radio wave transmitter are arranged. Enter tire pressure sensor.
(5) The casting curable resin composition according to any one of (1) to (3) above is injected into a mold in which a pressure sensor and a radio wave transmitter are arranged, and is cured and taken out from the mold. Caseless tire pressure sensor that can be obtained by:
(6) The caseless tire pressure sensor according to (5), wherein the curable resin is polyisocyanate.

  The curable resin composition for casting of the present invention is less susceptible to glass balloon separation and gelation, has a low viscosity, and can be a lightweight cured product.

Hereinafter, the present invention will be described in detail.
First, the casting curable resin composition of the present invention will be described in detail below.
The casting curable resin composition of the present invention comprises:
A curable resin composition for casting having a main agent containing a curable resin and an additive containing a curing agent and / or a curing catalyst,
At least one of the main agent and the additive includes a chain saturated hydrocarbon group-containing glass balloon that can be obtained by reacting a glass balloon with a silicon atom-containing compound represented by the following formula (1):
The amount of the chain saturated hydrocarbon group-containing glass balloon is 1 to 30 parts by mass with respect to a total of 100 parts by mass of the curable resin and the curing agent and / or curing catalyst. It is a thing.

(R ¹ O) _m -Si-R ² _4-m (1)

In the formula, each R ¹ independently represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and each R ² independently represents a monovalent chain having 3 or more carbon atoms which may contain a hetero atom. Represents a saturated hydrocarbon group, and m is an integer of 1 to 3.

The main agent will be described.
The main agent used in the curable resin composition for casting of the present invention contains a curable resin.
The curable resin contained in the main agent is not particularly limited as long as it is used as, for example, a potting material, a casting material, a sealing agent for electronic and electrical equipment, and an adhesive. Specific examples include reactive polyorganosiloxane, epoxy resin, polyisocyanate, and olefin compound.
Of these, reactive polyorganosiloxanes and olefin compounds are preferred from the viewpoints of curability, lighter weight, fluidity, and electrical insulation.
Moreover, polyisocyanate and an epoxy resin are preferable from the viewpoints of curability, lighter weight, fluidity, impact resistance, hardness of the cured product, and adhesiveness.

The reactive polyorganosiloxane that can be used as the curable resin is not particularly limited as long as it is a polyorganosiloxane having two or more reactive functional groups.

Examples of the reactive functional group include a hydrolyzable functional group, a hydroxy group, an alkenyl group, and a hydrosilyl group.
Examples of the hydrolyzable group include alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group; substituted alkoxy groups such as 2-methoxyethoxy group and 2-ethoxyethoxy group; enoxy groups such as isopropenoxy group. An acyloxy group such as an acetoxy group or an octanoxy group; a ketoxymato group such as a dimethylketooxymato group, a methylethylketooxymato group, a diethylketooxymato group, a methylbutylketooxymato group, or an ethylbutylketooxymato group; Amino groups such as amino group, methylethylamino group, diethylamino group, methylbutylamino group; amide groups such as acetamide group, N-methylacetamide group; methylethylaminoxy group, diethylaminoxy group, ethylbutylaminoxy group Replacement like Minokishi group; N- methylacetamide-substituted carbonylamino group such as an amino group; butylamino group and a substituted amino group such as cyclohexylamino group.

  Examples of the reactive polyorganosiloxane include polyorganosiloxane represented by the formula (2).

In the formula, each R ³ independently represents a monovalent hydrocarbon group that may have a functional group, and each R ⁴ independently represents a monovalent hydrocarbon group that may have a functional group. X is independently at least one selected from the group consisting of a hydrolyzable group, a hydroxy group, an alkenyl group and a hydrosilyl group, p is an integer of 1 to 3, and n is It is an integer of 1 to 2,000.

R ³ each independently represents a monovalent hydrocarbon group which may have a functional group. Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group; a cyclopentyl group and a cyclohexyl group. Cycloalkyl groups such as these; alkenyl groups such as vinyl groups and allyl groups; aryl groups such as phenyl groups, tolyl groups, and xylyl groups; and aralkyl groups such as 2-phenylethyl groups and 2-phenylpropyl groups. .
The monovalent hydrocarbon group can have a functional group. Examples of the functional group include a halogen atom such as a chlorine atom and a bromine atom; and a cyano group. Examples of the monovalent hydrocarbon group having a functional group include halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, and bromomethyl group; 3-cyanopropyl And cyanoalkyl groups such as groups.

Several R < ³ > in Formula (2) may mutually be same, or may differ. Of all the R ³ contained in the polyorganosiloxane represented by the formula (2), 85% or more is methyl, which is easy to synthesize and has a degree of polymerization that gives good physical properties after curing. Is preferred from the viewpoint of low viscosity, more preferably all methyl.

R ³ is preferably a phenyl group from the viewpoint of heat resistance, radiation resistance, cold resistance and transparency. From the viewpoint of oil resistance and solvent resistance, 3,3,3-trifluoropropyl group and 3-cyanopropyl group are preferable. From the viewpoint of providing a surface having paintability, a long-chain alkyl group or an aralkyl group is preferable. For R ³ , these groups can be used in combination with a methyl group.

R ⁴ each independently represents a monovalent hydrocarbon group which may have a functional group. R ⁴ may be the same as or different from R ³ . R ⁴ can be exemplified by the same as R ³ . Of these, a methyl group and a vinyl group are preferable from the viewpoint of reactivity.

Each X is independently at least one selected from the group consisting of a hydrolyzable group, a hydroxy group, an alkenyl group, and a hydrosilyl group.
Examples of the hydrolyzable group are the same as described above.
Among these, X is preferably a hydroxy group, an alkoxy group, an acyloxy group, or a methylethylketooxymato group, and particularly preferably a methoxy group, from the viewpoints of handleability and reactivity. X may be the same as or different from each other.

p is an integer of 1 to 3.
When X is a hydroxy group, p is preferably 1 from the viewpoints of curability, viscosity, and handleability.
The production method of the polyorganosiloxane in which X is a hydroxy group is not particularly limited. For example, a polyorganosiloxane can be produced by ring-opening polymerization or ring-opening copolymerization of a cyclic diorganosiloxane monomer such as octamethylcyclotetrasiloxane with an acidic catalyst or an alkaline catalyst in the presence of water. it can. A hydroxy group bonded to a silicon atom is introduced into the terminal of the obtained polyorganosiloxane.

When X is a hydrolyzable group, p is preferably 1 from the viewpoints of curability, viscosity, and handleability. The production method of the polyorganosiloxane in which X is a hydrolyzable group is not particularly limited. For example, it can be synthesized by condensing a polyorganosiloxane having a hydroxy group at the terminal and a silane having two or more hydrolyzable groups.

  n is an integer of 1 to 2,000. For n, the viscosity of the base polymer at 25 ° C. is in the range of 0.02 to 1,000 Pa · s, preferably 0.5 to 200 Pa · s from the viewpoints of elongation after curing, workability, and fluidity. You can choose to be. From the viewpoints of fluidity, viscosity, and cured product properties, n is preferably 13 to 2,000.

  A commercially available product can be used as the reactive polyorganosiloxane. Examples of commercially available products of reactive polyorganosiloxane include ELASTOSIL RT601A, ELASTOSIL RT604A, and ELASTOSIL RT745SA manufactured by Asahi Kasei Wacker Silicone.

  The polyisocyanate that can be used as the curable resin is not particularly limited as long as it is a compound having two or more isocyanate groups in one molecule. Examples of the polyisocyanate include low-molecular polyisocyanates and urethane prepolymers. Examples of the polyisocyanate include those in which an isocyanate group is bonded to an aliphatic hydrocarbon and those in which an isocyanate group is bonded to an aromatic ring. Among these, low molecular weight polyisocyanates in which isocyanate groups are bonded to aromatic rings, and isocyanate groups are bonded to aromatic rings from the viewpoint of rapid adhesion development, impact resistance, cured product hardness, and reactivity. A urethane prepolymer is preferred.

  Examples of the aromatic ring include benzene; condensed polycyclic hydrocarbons such as naphthalene and anthracene; and heterocyclic rings such as furan, thiophene, pyrrole, and pyridine. One of the preferred embodiments is that the aromatic ring is benzene because it is easily available. The aromatic ring can have a functional group other than an isocyanate group. There are no particular limitations on the type, position, and number of functional groups.

  Examples of the low-molecular polyisocyanate having an isocyanate group bonded to an aromatic ring include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), crude MDI (CrudeMDI), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate , Tolidine diisocyanate (TODI) and 1,5-naphthalene diisocyanate (NDI). Among these, 4,4′-MDI, 2,4′-MDI, crude MDI, polymethylene polyphenylene polyisocyanate, and 1,5-NDI are preferable from the viewpoint of impact resistance, cured product hardness, and reactivity. preferable. Crude MDI is a mixture containing two or more compounds represented by the following formula (3).

  In the formula, n is an integer of 0 or more.

  Examples of the urethane prepolymer having a structure in which an isocyanate group is bonded to an aromatic ring include a reaction product of the above low-molecular polyisocyanate and a polyol compound. The polyol compound is not particularly limited, and examples thereof include polyether polyols such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxypropylene triol, polyester polyols, acrylic polyols, polycarbonate polyols, other polyols, and mixed polyols thereof. Can be mentioned.

  The combination of a polyol compound and said low molecular polyisocyanate is not specifically limited. Each of the polyol compounds and each of the above low-molecular polyisocyanates can be used in any combination. Specifically, for example, at least one selected from the group consisting of polyoxyethylene glycol, polyoxypropylene glycol and polyoxypropylene triol, and selected from the group consisting of TDI, MDI, polymethylene polyphenylene polyisocyanate and crude MDI. A urethane prepolymer obtained from at least one kind is preferred from the viewpoints of impact resistance, hardness of the cured product, viscosity, storage stability, availability, and reactivity.

  The mixing ratio of the polyol compound and the low molecular polyisocyanate is such that the molar ratio of the isocyanate group in the low molecular polyisocyanate to the hydroxy group in the polyol compound (NCO / OH) is 1.3 to 2.5. It is preferable that it is, and it is more preferable that it is 1.5-2.0. When it is in such a range, the viscosity of the urethane prepolymer obtained is moderate and the cured product is excellent in elongation.

  The reaction between the polyol compound and the low molecular weight polyisocyanate is not particularly limited. For example, the method of manufacturing by heating and stirring the polyol compound of said amount ratio and said low molecular weight polyisocyanate at 50-100 degreeC is mentioned. If necessary, for example, a urethanization catalyst such as an organic tin compound, an organic bismuth, or an amine can be used.

The polyisocyanate is preferably liquid at room temperature from the viewpoint of handleability. In addition to the isocyanate group, the polyisocyanate can have a group such as a hydroxy group, an acid anhydride group, an amino group, a latent amino group, a mercapto group, or a carboxy group in the molecule. When having such a group that can be cross-linked by reacting with an isocyanate group, the crosslink density of the obtained cured product is improved and the physical properties are excellent.
A curable resin can be used individually or in combination of 2 types or more, respectively.

The additive will be described below.
The additive used for the curable resin composition for casting of the present invention contains a curing agent and / or a curing catalyst.
The curing agent contained in the additive is not particularly limited as long as it can react with the curable resin. For example, silicon compounds having hydrolyzable groups and / or partial hydrolysis condensates thereof, polyols, amine-based curing agents, acid or acid anhydride-based curing agents, basic active hydrogen compounds, imidazoles, polymercaptan-based curing agents And phenolic resin. A hardening | curing agent can be selected according to the kind of curable resin.

  Among these, the curing agent for reactive polyorganosiloxane easily reacts with the reactive functional group of reactive polyorganosiloxane, and has a hydrolyzable group-containing silicon compound and / or part thereof from the viewpoint of curability and adhesiveness. A hydrolysis-condensation product is preferred. As a silicon compound which has a hydrolysable group, the silicon compound represented by following formula (4) is mentioned, for example.

R ⁵ _4-q -Si-X _q (4)

In the formula, each R ⁵ independently represents a monovalent hydrocarbon group which may have a functional group,
Is as defined above, and q is an integer of 2 to 4.

R ⁵ each independently represents a monovalent hydrocarbon group which may have a functional group.
Examples of the monovalent hydrocarbon group include those described above. Of these, a methyl group and a vinyl group are preferable from the viewpoint of curability.
Examples of the functional group include an amino group, an imino group, an epoxy group, an isocyanate group, an acryloxy group, a methacryloxy group, a mercapto group, and a halogen atom (for example, a chlorine atom and a bromine atom).
Examples of the monovalent hydrocarbon group having a functional group include at least one selected from the group consisting of an amino group, an imino group, an epoxy group-containing group, an isocyanate group, an acryloxy group, a methacryloxy group, a mercapto group, and a halogen atom. Examples include a substituted alkyl group or a phenyl group. Examples of the alkyl group having a functional group include a methyl group having the above functional group, a propyl group having a functional group at the 3-position, and a butyl group having a functional group at the 4-position.

  Examples of the curing agent for reactive polyorganosiloxane include tetramethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, and phenyltriethoxysilane. , Tetrapropoxysilane, tetraisopropoxysilane and alkoxy group-containing compounds such as partially hydrolyzed condensates thereof; tetrakis (2-ethoxyethoxy) silane, methyltris (2-methoxyethoxy) silane, vinyl (2-ethoxyethoxy) Substituted alkoxy group-containing compounds such as silane, phenyltris (2-methoxyethoxy) silane and partial hydrolysis condensates thereof; methyltriisopropenoxysilane, vinyltriisopropenoxy Silane, phenyl tri isopropenoxysilane silane, dimethyl isopropenoxysilane silane include enoxy group-containing compounds such as methyl vinyl di- isopropenoxysilane silane and their partially hydrolyzed condensates.

  Further, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriisopropoxysilane, 3-aminopropyltriacetamidosilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N, N-dimethyl-3 -Amino group-containing silane such as aminopropyltrimethoxysilane; epoxy group-containing such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane Silane; 3-iso Isocyanato group-containing silanes such as anatopropyltrimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane; 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3 A (meth) acryloxy group-containing silane such as methacryloxypropylmethyldimethoxysilane; a mercapto group-containing silane such as 3-mercaptopropyltrimethoxysilane; a halogen atom-containing silane such as 3-chloropropyltrimethoxysilane; Silanes and their partial hydrolysis condensates are mentioned.

  Among them, the curing agent for reactive polyorganosiloxane is tetramethoxysilane, tetraethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane and partial hydrolysis condensates thereof from the viewpoint of fluidity, viscosity and curability; aminoalkyl Preferred are group-containing silanes, (alkyl) acryloxy group-containing silanes, and polyhydrosilanes.

  A commercially available product can be used as the curing agent for the reactive polyorganosiloxane. Examples of the curing agent for the reactive polyorganosiloxane include ELASTOSIL RT601B, ELASTOSIL RT604B, and ELASTOSIL RT745SB manufactured by Asahi Kasei Wacker Silicone.

  Examples of the curing agent that can be used for the polyisocyanate include polyols, amine-based curing agents, acid or acid anhydride-based curing agents, basic active hydrogen compounds, imidazoles, polymercaptan-based curing agents, and phenol resins. It is done. Of these, amine-based curing agents and polyols are preferred from the viewpoints of reactivity and physical properties of the cured product.

  Examples of the amine curing agent include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, iminobispropylamine, bis (hexamethylene) triamine, and 1,3,6-trisaminomethylhexane. Polyamines; polymethylenediamines such as trimethylhexamethylenediamine, polyetherdiamine, diethylaminopropylamine; mensendiamine (MDA), isophoronediamine (IPDA), bis (4-amino-3-methylcyclohexyl) methane, N -Aminoethylpiperazine (N-AEP), diaminodicyclohexylmethane, bisaminomethylcyclohexane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxas [5] undecane, a cyclic aliphatic polyamine such as a diamine having a norbornane skeleton represented by NBDA manufactured by Mitsui Chemicals; an aliphatic polyamine containing an aromatic ring such as metaxylylenediamine (MXDA); Aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane and their derivatives.

  Examples of amine curing agents include Mannich-modified diamine obtained by reacting polyamine with aldehyde and / or phenol; amine adduct (polyamine epoxy resin adduct), polyamine-ethylene oxide adduct, polyamine-propylene oxide adduct, cyanoethyl. Polyamine, ketimine which is a reaction product of aliphatic polyamine and ketone; tetramethylguanidine, piperidine, pyridine, benzyldimethylamine, picoline, 2- (dimethylaminomethyl) phenol, dimethylcyclohexylamine, dimethylbenzylamine, dimethylhexylamine , Dimethylaminophenol, dimethylamino-p-cresol, N, N′-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] o Secondary or tertiary amines such as tan, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0] -7-undecene; triethanolamine Alkanolamines such as N, N′-tetra (2-hydroxypropyl) ethylenediamine; liquid polyamides obtained by reacting dimer acid with polyamines such as diethylenetriamine and triethylenetetramine.

  The polyol compound used as a curing agent for polyisocyanate is not particularly limited, and examples thereof include polyether polyol, polyester polyol, acrylic polyol, polycarbonate polyol, other polyols, and mixed polyols thereof.

  Examples of the polyether polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol, 1,3-butanediol, 1, One or more polyhydric alcohols such as 4-butanediol, 4,4'-dihydroxyphenylpropane, 4,4'-dihydroxyphenylmethane, pentaerythritol, propylene oxide, ethylene oxide, butylene oxide, styrene Examples include polyether polyols obtained by adding one or more alkylene oxides such as oxides; polyether polyols obtained by ring-opening polymerization such as tetrahydrofuran.

  Specific polyether polyols include, for example, polytetramethylene glycol obtained by ring-opening polymerization of polyoxyethylene glycol (for example, triethylene glycol), polyoxypropylene glycol, polyoxypropylene triol, and tetrahydrofuran.

  Examples of the polyester polyol include one or more low molecular polyols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, and 1,1,1-trimethylolpropane. And a condensation polymer of glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid and one or more of low molecular weight carboxylic acids and oligomeric acids; propionlactone, valerolactone , Ring-opening polymers of lactones such as caprolactone.

  Examples of the acrylic polyol include acrylic polyols that can be obtained from at least one selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and β-hydroxyethyl methacrylate. Can be mentioned.

  Examples of the polycarbonate polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1, One or more diols such as 9-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, dimethyl carbonate, diphenyl What can be obtained by making at least 1 sort (s) of carbonate, ethylene carbonate, and phosgene react is mentioned.

  Examples of other polyols include polymer polyols; polybutadiene polyols; hydrogenated polybutadiene polyols; and low molecular polyols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, and hexanediol. .

  Among these, as a curing agent for polyisocyanate, triethylene glycol, N, N′-tetra (2-hydroxypropyl) ethylenediamine, polybutadiene polyol, polyoxypropylene glycol, polyoxypropylene are preferable from the viewpoints of workability and handleability. Triol is preferred. In particular, from the viewpoint of physical properties of the cured product, at least one selected from the group consisting of triethylene glycol, N, N′-tetra (2-hydroxypropyl) ethylenediamine, and polybutadiene polyol is preferable.

  Moreover, since the polyol compound has excellent physical properties after curing, a polyether polyol having a number average molecular weight of 1500 to 15000 is preferable, and a polyether polyol having 2000 to 10,000 is more preferable.

The combination of the polyisocyanate and the polyisocyanate curing agent is not particularly limited. Each of the polyisocyanates and each of the polyisocyanate curing agents can be used in any combination. Specifically, for example, the polyisocyanate is at least one selected from the group consisting of TDI, XDI, MDI, polymethylene polyphenylene polyisocyanate and crude MDI, and the curing agent is triethylene glycol, N, N′-tetra ( 2-hydroxypropyl) ethylenediamine, polybutadiene polyol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxypropylene triol, and a combination that is at least one selected from the group consisting of polyoxypropylene tetraol, impact resistance, cured product From the viewpoint of hardness and reactivity.
A hardening | curing agent can be used individually or in combination of 2 or more types, respectively.

The content of the curing agent is not particularly limited, and is not particularly limited as long as it is an amount capable of curing the curable resin.
Specifically, the amount of the curing agent used for the reactive polyorganosiloxane is preferably 1 to 1,000 parts by mass with respect to 100 parts by mass of the reactive polyorganosiloxane from the viewpoint of mixing properties. More preferably, it is -500 mass parts.

  The amount of the curing agent used relative to the polyisocyanate is preferably such that the molar ratio of the isocyanate group in the polyisocyanate to the functional group in the curing agent (NCO / functional group of the curing agent) is 1.3 to 2.5. More preferably, it is .5 to 2.0. In such a range, the workability, the stability of the physical properties of the cured product, and the adhesiveness are excellent.

The curing catalyst will be described below.
The curing catalyst contained in the additive is not particularly limited as long as it can react with the curable resin. For example, a metal catalyst, an amine catalyst, imidazoles (for example, 2-methylimidazole), and a phosphorus catalyst (for example, triphenylphosphine, tetraphenylphosphonium tetraphenylborate) can be used. The curing catalyst can be selected according to the curable resin.

Curing catalysts that can be used for reactive polyorganosiloxane include, for example, platinum catalysts; cobalt octoate, manganese octoate, iron octoate, zinc octoate, tin octoate, tin naphthenate, tin caprylate, Carboxylic acid metal salts such as tin oleate; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, dibutyltin dimethoxide, diphenyltin diacetate, dibutylbis (triethoxysiloxy) tin, dibutylbis (acetylacetonato) tin Organotin compounds such as dioctyltin dilaurate; tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, 1,3-propanedioxytitanium bis (ethylacetylacetate) Alkoxy titaniums such as: aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate, triethoxyaluminum and other organoaluminum; zirconium tetraacetylacetonate, tetraisopropoxyzirconium, tetrabutoxyzirconium, tributoxy Organic zirconium compounds such as zirconium acetylacetonate and tributoxyzirconium stearate; titanium chelate compounds such as diisopropoxybis (ethylacetylacetato) titanium; amine compounds; quaternary ammonium compounds.
Of these, organotin compounds, alkoxytitaniums, and platinum catalysts are preferable from the viewpoint of having a small amount and a large catalytic ability.
Of these, non-conductive is preferable from the viewpoint of electrical insulation.

  Examples of the curing catalyst that can be used for the polyisocyanate include a metal catalyst and an amine catalyst. Examples of the metal catalyst include dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, dibutyltin dimethoxide, diphenyltin diacetate, dibutylbis (triethoxysiloxy) tin, dibutylbis (acetylacetonato) tin, dioctyltin dilaurate Organotin compounds such as: tetrabutyl titanate, titanates such as tetrapropyl titanate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium Chelate compounds such as tetraacetylacetonate and titanium tetraacetylacetonate; octanoic acid , Octane acid metal salts such as bismuth octoate.

  Examples of the amine catalyst include monoamines such as butylamine, octylamine, dibutylamine, triethylamine, N, N-dimethylcyclohexylamine; N, N, N ′, N′-tetramethylethylenediamine, N, N, N Diamines such as', N'-tetramethylpropane-1,3-diamine, N, N, N ', N'-tetramethylhexane-1,6-diamine; N, N, N', N ", Triamines such as N ″ -pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyldipropylenetriamine; N-methylmorpholine, N, N′-dimethylpiperazine, N-methyl-N ′ Cyclic amines such as-(2-dimethylamino) -ethylpiperazine, 1,4-diazabicyclo [2.2.2] octane; Alcohol amines such as aminoethanol, dimethylaminoethoxyethanol, N, N, N′-trimethylaminoethylethanolamine; bis (2-dimethylaminoethyl) ether, ethylene glycol bis (3-dimethyl) aminopropylether And ether amines or their salt compounds.

Among the curing catalysts that can be used for the polyisocyanate, an organic tin compound such as dibutyltin diacetate, 1,4-diazabicyclo [2.2.2] can be obtained with a small amount of use. ] Octane is preferred.
The curing catalysts can be used alone or in combination of two or more.

The amount of the curing catalyst used is not particularly limited, and can be used in an amount that can sufficiently cure the curable resin.
Specifically, the amount of the reactive polyorganosiloxane curing catalyst used is 0.01 to 20 parts by mass with respect to 100 parts by mass of the reactive polyorganosiloxane from the viewpoint of curing speed and physical properties of the cured product. Is preferable, and it is more preferable that it is 0.1-10 mass parts.

  The amount of the polyisocyanate curing catalyst used is preferably 0.01 to 20 parts by mass, and 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyisocyanate from the viewpoint of curing speed and physical properties of the cured product. More preferred.

The chain saturated hydrocarbon group-containing glass balloon will be described below.
The chain saturated hydrocarbon group-containing glass balloon contained in the casting curable resin composition of the present invention is obtained by reacting a glass balloon with a silicon atom-containing compound represented by the following formula (1). It can be.

(R ¹ O) _m -Si-R ² _4-m (1)

In the formula, each R ¹ independently represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and each R ² independently represents a monovalent chain having 3 or more carbon atoms which may contain a hetero atom. Represents a saturated hydrocarbon group, and m is an integer of 1 to 3.

  The glass balloon used in the production of the chain saturated hydrocarbon group-containing glass balloon is not particularly limited as long as it is a glass hollow body. The average particle diameter of the glass balloon is preferably 20 to 60 μm and more preferably 30 to 50 μm from the viewpoint of mechanical strength and low specific gravity. The bulk density of the glass balloon is preferably 0.1 to 0.4 g / ml from the viewpoints of mechanical strength and low specific gravity. Moreover, it is preferable that the average shell thickness of a glass balloon is 2-4 micrometers from a viewpoint of mechanical strength.

Examples of the glass balloon include a temperature of 500 to 700 ° C., preferably 550 to 650 ° C., a pressure of 0.1 × 10 ^{6 to} 0.6 × 10 ⁶ Pa, and preferably 0.1 × 10 ^{6 to} 0.4 × 10. What was baked for 5 to 120 minutes on the conditions of ⁶ Pa, preferably nitrogen atmosphere can be used. Further, a glass balloon that has been surface-treated with an acid can be used.

  The silicon atom-containing compound used in the production of the chain saturated hydrocarbon group-containing glass balloon is a compound represented by the following formula (1).

(R ¹ O) _m -Si-R ² _4-m (1)

In the formula, each R ¹ independently represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and each R ² independently represents a monovalent chain having 3 or more carbon atoms which may contain a hetero atom. Represents a saturated hydrocarbon group, and m is an integer of 1 to 3.

R ¹ each independently represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. The alkyl group preferably has 1 to 5 carbon atoms. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, An isopentyl group is mentioned. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. As an aralkyl group, for example,
Examples include a benzyl group and a phenethyl group. Among them, from the viewpoint of reactivity, R ¹ is preferably a methyl group, all of R ¹ is more preferably a methyl group.

R ² each independently represents a monovalent chain saturated hydrocarbon group having 3 or more carbon atoms, which may contain a hetero atom.
The number of carbon atoms is preferably 3 to 20 and more preferably 3 to 15 from the viewpoints of dispersibility with respect to the curable resin and dispersion stability.
Examples of the chain saturated hydrocarbon group include linear or branched ones. Specifically, for example, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-heptyl group N-octyl group, n-nonyl group, 2-ethylhexyl group, n-decyl group. Of these, an n-hexyl group and an n-decyl group are preferable from the viewpoint of ease of availability because the glass balloon is more difficult to separate.

  Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom. Examples of the group formed by a hetero atom include a functional group such as a carbonyl group and a urea group (carbamide group); a bond such as an ether bond, an ester bond, an amide bond, and a urethane bond.

The hetero atom can be present in the main chain of the chain saturated hydrocarbon group or between the silicon atom and the chain saturated hydrocarbon group in the formula (1). The hetero atom does not exist at the terminal opposite to the terminal where the chain saturated hydrocarbon group is bonded to the silicon atom. That is, the silicon atom-containing compound used in the production of the chain saturated hydrocarbon group-containing glass balloon does not have a functional group at the end of the chain saturated hydrocarbon group. A chain saturated hydrocarbon group-containing glass balloon that can be obtained by reacting such a silicon atom-containing compound with a glass balloon is less likely to react with other components in the casting curable resin composition. , Hardly gelled, excellent in storage stability and dispersion stability.
As the chain saturated hydrocarbon group containing a hetero atom, for example, —CH ₂ CH ₂ CH ₂ —NH—C (═O) O— (CH ₂ CH ₂ CH ₂ ) _n —OR (for example, R is a methyl group) Represents an ethyl group, and n represents an integer of 1 to 5.), and a reaction product of isocyanate silane and monoalcohol.

R ² can be appropriately selected in consideration of the affinity for the curable resin. For example, when the curable resin is a reactive polyorganosiloxane, R ² is preferably an n-hexyl group or an n-decyl group. Further, when the curable resin is a polyisocyanate, R ² represents —CH ₂ CH ₂ CH ₂ —NH—C (═O) O— (CH ₂ CH ₂ CH ₂ ) _n —OR (for example, R represents a methyl group or an ethyl group, and n represents an integer of 1 to 5.

Examples of the silicon atom-containing compound include n-hexyltrimethoxysilane, (CH ₃ 0) ₃ —Si—CH ₂ CH ₂ CH ₂ —NH—C (═O) O— (CH ₂ CH ₂ CH ₂ ) _n -OCH ₃ (n = 2), include the reaction product of an isocyanate silane and monoalcohol.

  The usage-amount of the silicon atom containing compound represented by Formula (1) is 10-1,000 mass parts with respect to 100 mass parts of glass balloons from a viewpoint of a dispersibility, a mixing property, workability | operativity, and handleability. Is preferable, and it is more preferable that it is 100-500 mass parts.

  The production of the chain saturated hydrocarbon group-containing glass balloon is not particularly limited, and for example, the glass balloon and a silicon atom-containing compound represented by the formula (1) may be mixed and stirred. Moreover, in order to accelerate | stimulate reaction, it can heat. For example, when n-hexyltrimethoxysilane is used, a method of heating and stirring at 50 to 150 ° C. for 24 to 48 hours can be mentioned.

  The case where the silicon atom-containing compound represented by the formula (1) is n-hexyltrimethoxysilane will be described below as an example of the reaction between the glass balloon and the silicon atom-containing compound represented by the formula (1). . In addition, reaction of a glass balloon and the silicon atom containing compound represented by Formula (1) is not limited to the following examples.

In the formula (I), (a) represents n-hexyltrimethoxysilane, and (b) represents one of a plurality of silanol groups present on the surface of the glass balloon.
In formula (I), the methoxy group of n-hexyltrimethoxysilane (a) undergoes an alcohol exchange reaction with the silanol group (b) on the surface of the glass balloon to form a new siloxane bond (c). Through such a reaction, the glass balloon can contain an n-hexyl group.
One n-hexyltrimethoxysilane (a) may react with the silanol group (b) at at least one location on the surface of one glass balloon. In such a case, the resulting glass balloon contains at least one n-hexyl group.

Examples of the chain saturated hydrocarbon group-containing glass balloon include, for example, a glass balloon, glass balloon, and (CH ₃ O) containing an n-hexyl group that can be obtained by reacting a glass balloon with n-hexyltrimethoxysilane. _3- Si—CH ₂ CH ₂ CH ₂ —NH—C (═O) O— (CH ₂ CH ₂ CH ₂ ) _n —OCH ₃ (n = 2) can be obtained by reacting with —Si— ( A glass balloon containing OCHO) ₂ —CH ₂ CH ₂ CH ₂ —NH—C (═O) O— (CH ₂ CH ₂ CH ₂ ) _n —OCH ₃ (n = 2) may be mentioned. Among them, separation of glass balloons is less likely to occur, it is difficult to gel, low viscosity, and can be a light cured product. Therefore, n- can be obtained by reacting glass balloons with n-hexyltrimethoxysilane. Glass balloons containing hexyl groups are preferred.
The chain-like saturated hydrocarbon group-containing glass balloons can be used alone or in combination of two or more.

  The amount of the chain saturated hydrocarbon group-containing glass balloon is 1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the curable resin and the curing agent and / or the curing catalyst. In such a range, the viscosity, mechanical strength, impact resistance, workability, and specific gravity are excellent. Furthermore, since it is excellent in such an effect, the amount of the chain saturated hydrocarbon group-containing glass balloon is 5 to 30 parts by mass with respect to 100 parts by mass of the total amount of the curable resin and the curing agent and / or the curing catalyst. It is preferable that it is 10-30 mass parts.

  In the curable resin composition for casting of the present invention, the chain-like saturated hydrocarbon group-containing glass balloon is contained in at least one of the main agent and the additive. Especially, it is preferable that a chain-like saturated hydrocarbon group containing glass balloon is contained in both a main ingredient and an additive from a mixed viewpoint with a main ingredient and an additive. When the chain saturated hydrocarbon group-containing glass balloon is contained in both the main agent and the additive, the chain saturated hydrocarbon group-containing glass balloon contained in the main agent is 5-30 with respect to 100 parts by mass of the curable resin. It is preferable that it is a mass part, and it is more preferable that it is 10-30 mass parts. Moreover, it is preferable that the chain saturated hydrocarbon group containing glass balloon contained in an additive is 5-30 mass parts with respect to 100 mass parts of total amounts of a hardening | curing agent and a curing catalyst, and is 10-30 mass parts. More preferably. In such a range, since the viscosity of the main agent and the additive is approximately the same or close to each other, the mixing property of the main agent and the additive is excellent.

The viscosity of the main agent is preferably 20 Pa · S or less, as measured by an E-type viscometer under the condition of 20 ° C., from the viewpoint of mixing property, fluidity, and dischargeability. It is more preferable that
The viscosity of the additive is preferably 10 Pa · S or less, as measured by an E-type viscometer under the condition of 20 ° C., from the viewpoint of mixing property, fluidity, and dischargeability, and 0.01 to 5 Pa · S is more preferable.

  In the cast resin curable resin composition of the present invention, in addition to the curable resin, the curing agent and / or the curing catalyst, and the chain saturated hydrocarbon group-containing glass balloon, the scope of the present invention is not impaired. A compounding agent can be contained. Examples of the compounding agent include fillers, plasticizers, antioxidants, antioxidants, inorganic pigments, organic pigments, adhesion imparting agents, flame retardants, dehydrating agents, solvents, thixotropy imparting agents, and antistatic agents. The amount of the compounding agent is not particularly limited, and an amount that can be generally used in the curable resin composition for casting can be blended. A compounding agent can be used individually or in combination of 2 or more types, respectively. The compounding agent is usually contained in the additive, but can be contained in the main agent according to the use and necessity.

  Examples of the filler include fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; calcium carbonate, magnesium carbonate, zinc carbonate Waxy clay, kaolin clay, calcined clay; carbon black; and these fatty acids, resin acids, fatty acid esters, and urethane compound treated products.

  Examples of the plasticizer include diisononyl adipate, dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, dioctyl adipate, isodecyl succinate, diethylene glycol dibenzoate, pentaerythritol ester, butyl oleate, methyl acetylricinoleate, tricresyl phosphate, phosphorus Examples include trioctyl acid, propylene glycol adipate polyester, and butylene glycol polyester adipate.

Examples of the antioxidant include butylhydroxytoluene, butylhydroxyanisole, and triphenyl phosphite.
Examples of the antiaging agent include hindered phenol compounds, benzotriazole compounds, and hindered amine compounds.

Examples of inorganic pigments include titanium dioxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, and sulfate.
Examples of organic pigments include azo pigments and copper phthalocyanine pigments.
Examples of the adhesion imparting agent include terpene resin, phenol resin, terpene-phenol resin, rosin resin, and xylene resin.

Flame retardants include, for example, chloroalkyl phosphate, methylphosphonic acid dimethyl ester, bromine and / or phosphorus atom-containing compounds, ammonium polyphosphate, diethyl bishydroxyethyl aminoethyl phosphate, neopentyl bromide-polyether, brominated poly Ether.
Examples of the dehydrating agent include acyloxysilyl group-containing polysiloxane.

  The method for preparing the casting curable resin composition of the present invention is not particularly limited. For example, a chain-saturated hydrocarbon group-containing glass balloon is added to both the main agent containing the curable resin and the additive containing the curing agent and / or the curing catalyst. And kneading method. After kneading, the main agent and the additive are stored separately in a sealed container replaced with an inert gas such as nitrogen gas, for example, and the main agent and the additive can be used by thoroughly mixing them during use.

  The curable resin composition for casting of the present invention can be cured by moisture in the air or the like. The curing temperature of the curable resin composition for casting of the present invention is determined from the viewpoint of curing speed, or the curable resin composition for casting of the present invention is used as a curable resin composition for casting for a tire pressure sensor. When it does, it is preferable that it is 20-120 degreeC from a viewpoint of the lifetime of a battery, and it is more preferable that it is 20-100 degreeC.

For example, when a reactive polyorganosiloxane is used as the curable resin, the reactive polyorganosiloxane and an additive containing a curing agent and / or a curing catalyst are mixed at room temperature (for example, 5 to 35 ° C.) and cured. Can be made.
Moreover, when using polyisocyanate as curable resin, the method of heating and stirring a polyisocyanate and the additive containing a hardening | curing agent and / or a hardening catalyst at 5-100 degreeC is mentioned.

The hardness of the cured product obtained by curing the curable resin composition for casting of the present invention is preferably 60 or more in terms of JIS A hardness from the viewpoint of impact resistance. From the viewpoint of impact resistance and mechanical strength, the hardness after curing is preferably 80 or more, and more preferably 85 to 100. The JIS A hardness is a hardness measured according to JIS K6253-1997.
As a combination of the curable resin and the curing agent in which the hardness of the cured product is in such a range, for example, the curable resin is at least selected from the group consisting of TDI, XDI, MDI, polymethylene polyphenylene polyisocyanate, and crude MDI. One type of polyisocyanate, and the curing agent is triethylene glycol, N, N′-tetra (2-hydroxypropyl) ethylenediamine, polybutadiene polyol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxypropylene tetraol and polyoxy The combination which is at least 1 sort (s) of polyol chosen from the group which consists of propylene triols is mentioned. Among them, the curable resin is at least one polyisocyanate selected from the group consisting of MDI, polymethylene polyphenylene polyisocyanate and crude MDI, and the curing agent is triethylene glycol, N, N′-tetra (2-hydroxypropyl). ) A combination of ethylenediamine and polybutadiene polyol is preferable because the hardness becomes higher.

The present inventor speculated that the separation of the glass balloon in the conventional curable resin composition is caused by the large difference between the specific gravity of the glass balloon and the specific gravity of the curable resin. And this inventor conceived that a glass balloon becomes difficult to isolate | separate from a curable resin composition by improving affinity with components other than the glass balloon in a curable resin composition, and a glass balloon, In order to increase the affinity in the curable resin composition, the present inventors have found that the above-described chain saturated hydrocarbon group-containing glass balloon is suitable as the glass balloon.
In the curable resin composition for casting of the present invention, the chain saturated hydrocarbon group-containing glass balloon is difficult to separate even if the difference in specific gravity from the curable resin is large.
Thus, the chain saturated hydrocarbon group-containing glass balloon is difficult to separate in the composition because (1) the chain saturated hydrocarbon group is as long as 3 or more carbon atoms, and (2) the chain saturated hydrocarbon. Since the hydrogen group has a high affinity for the curable resin, and (3) the chain saturated hydrocarbon group is not contracted in the composition and is in a long extended state, the curable resin and the chain saturated hydrocarbon are obtained. This is because the compatibility with the group-containing glass balloon is improved and the chain saturated hydrocarbon group-containing glass balloon can be prevented from moving due to the difference in specific gravity in the composition. Guess.
For these reasons, the curable resin composition for casting of the present invention is excellent in dispersibility because the chain saturated hydrocarbon group-containing glass balloon is difficult to separate. Also, in the case where the chain saturated hydrocarbon group-containing glass balloon is separated, the separation rate is slow, so that after mixing the composition, the chain saturated hydrocarbon group-containing glass balloon is immediately separated in the composition. There is nothing, and it is excellent in storage stability.

Examples of the curable resin composition for casting of the present invention include potting materials, casting materials, sealing materials for electronic devices, adhesives, and sealing materials.
Further, by using the casting curable resin composition of the present invention as a potting material, a casting material, or a sealing material for electronic and electrical equipment as described above, for example, tire pressure sensors and speed sensors can be manufactured. it can.

Next, the cased tire pressure sensor of the present invention will be described.
The cased tire pressure sensor of the present invention is a tire pressure sensor that can be obtained by injecting and curing the casting curable resin composition of the present invention into a case in which a pressure sensor and a radio wave transmitter are arranged. .

  The casting curable resin composition used in the cased tire pressure sensor of the present invention is not particularly limited as long as it is the casting curable resin composition of the present invention. Among them, from the viewpoints of fluidity and electrical insulation, the curable resin is a reactive polyorganosiloxane, the curing agent is a polyhydrosilane, the curing catalyst is a platinum catalyst, and an n-hexyl group-containing glass. A balloon is preferred. The amount of each component used is the same as above.

  The cased tire pressure sensor of the present invention will be described below with reference to the accompanying drawings. The cased tire pressure sensor of the present invention is not limited to the attached drawings.

  FIG. 1 is a perspective view from the top side schematically showing the appearance of a cased tire pressure sensor. In FIG. 1, reference numeral 5 represents a cased tire pressure sensor. The case-equipped tire pressure sensor 5 has a lid-side case 6a and a base-side case 6b that are divided into two parts in the vertical direction. A part of the lid-side case 6a is tired by a pressure sensor (not shown). A small communication hole 9 is provided so as to detect the pressure inside (not shown). As the lid side case 6a and the base side case 6b, for example, those made of hard resin such as polybutylene terephthalate (PBT) can be used.

FIG. 2 is a perspective view from the bottom side schematically showing the appearance of the cased tire pressure sensor 5. The bottom surface 6x of the attachment portion in the longitudinal direction of the base-side case 6b can be a flat surface. However, it is preferable that the bottom surface 6x be curved so as to easily adhere to the curvature of a tire rim (not shown). As one.

  FIG. 3 is a side view schematically showing a side surface of the cased tire pressure sensor 5 viewed from the direction of the arrow in FIG. As shown in FIGS. 2 and 3, chamfered portions 6 y can be provided on both sides in the width direction of the cased tire pressure sensor 5 so as not to interfere with a rim flange (not shown).

Further, a plurality of protrusions 11 as shown in FIGS. 2 and 3 are provided on the bottom surface 6x of the attachment portion of the base side case 6b so as to be attached corresponding to rims (not shown) having various curvature shapes. It is possible. By providing this projection 11, it is possible to adjust the thickness of the adhesive means even when the curvature of the rim changes or when the shape changes, and it can be adapted to any form of rim mounting part. Can do. Examples of the shape of the protrusion 11 include pin-shaped protrusions, plate-shaped protrusions, and various other forms as shown in FIGS.

  FIG. 4 is a plan view schematically showing the appearance of the cased tire pressure sensor 5. Two communication holes 9 are provided in the lid side case 6a.

5 is a plan view schematically showing the internal structure of the cased tire pressure sensor 5. FIG. 6 is a cross-sectional view taken along the line AA of the cased tire pressure sensor 5 of FIG. 5, and FIG. It is BB sectional drawing of the tire pressure sensor 5 with a case of 5. FIG.
As shown in FIG. 5, a battery 7 and a base 8 are arranged in the base side case 6b. The base 8 includes a pressure sensor (not shown) and a radio wave transmitter (not shown).
As shown in FIG. 6, the lid side case 6 a and the base side case 6 b are connected by a plurality of connecting screws 10.
As shown in FIG. 7, the battery 7 and the base 8 are accommodated in the base-side case 6b via respective support members 9a and 9b.

As a method for producing a cased tire pressure sensor of the present invention, for example, as shown in FIG. 5, a battery 7 and a base 8 are arranged on a base side case 6b, and the casting curable resin composition of the present invention is used. It is poured onto the base 8 using a small amount discharge device (not shown), and the curable resin composition for casting according to the present invention is filled in a space indicated by a region 13 (region indicated by dots) in FIG. To fill. Thereafter, the composition in the base side case 6b is cured, for example, under conditions of 20 to 100 ° C. for 5 minutes to 24 hours, and after curing, the base side case 6b is covered with the lid side case 6a, The base side case 6b and the lid side case 6a are connected by the connecting screw 10 to produce a case-equipped tire pressure sensor.
The weight of the cased tire pressure sensor of the present invention is preferably 50 g or less per piece.

  The cased tire pressure sensor of the present invention can be attached to, for example, a part of a tire wheel using an adhesive means such as an adhesive or a double-sided adhesive tape.

Next, the caseless tire pressure sensor of the present invention will be described.
The caseless tire pressure sensor of the present invention is a tire that can be obtained by injecting and curing the curable resin composition for casting of the present invention into a mold in which a pressure sensor and a radio wave transmitter are arranged, and removing the mold from the mold. Air pressure sensor.

The casting curable resin composition used in the caseless tire pressure sensor of the present invention is not particularly limited as long as it is a casting curable resin composition of the present invention.
Among them, from the viewpoints of fluidity, impact resistance, cured product hardness, and handleability, the curable resin is preferably a polyisocyanate, and is superior in terms of rapid adhesion, impact resistance, and cured product hardness. From the viewpoint of reactivity, it is more preferable to use a low-molecular polyisocyanate in which an isocyanate group is bonded to an aromatic ring, such as 4,4′-MDI, 2,4′-MDI, crude MDI, polymethylene polyphenylene poly. More preferably, it is an isocyanate.
The curing agent is preferably a polyol compound from the viewpoint of workability and handleability, and is triethylene glycol, N, N′-tetra (2-hydroxypropyl) ethylenediamine, polybutadiene polyol, polyoxyethylene glycol, polyoxypropylene. More preferred are glycol, polyoxypropylene triol, and polyoxypropylene tetraol.

The combination of the curable resin and the curing agent is not particularly limited, and for example, at least one polyisocyanate selected from the group consisting of TDI, XDI, NDI, MDI, polymethylene polyphenylene polyisocyanate and crude MDI, and triethylene Curing of at least one selected from the group consisting of glycol, N, N′-tetra (2-hydroxypropyl) ethylenediamine, polybutadiene polyol, polyoxyethylene glycol, polyoxypropylene glycol and polyoxypropylene triol, polyoxypropylene tetraol A urethane prepolymer obtained from an agent is preferable from the viewpoint of impact resistance, hardness, and reactivity.
The curing catalyst is preferably a tin compound and / or an amine compound from the viewpoint of curability and blending amount.
The chain saturated hydrocarbon group-containing glass balloon is preferably a glass balloon containing an n-hexyl group from the viewpoints of dispersibility and availability.
The amount of each component used is the same as above.

As a manufacturing method of the caseless tire pressure sensor of the present invention, for example, a pressure sensor and a radio wave transmitter are arranged in a mold such as a mold, and then the casting curable resin of the present invention is placed in the mold. Examples thereof include a method in which the composition is sufficiently injected and then cured and removed from the mold. For example, the pressure sensor and the radio wave transmitter may be separately disposed in the mold, or may be disposed in the mold as a substrate incorporating the pressure sensor and the radio wave transmitter. Moreover, a battery can be further used as needed.
Further, when producing the caseless tire pressure sensor of the present invention, the curable resin composition for casting of the present invention is potted and cured on at least the pressure sensor and the radio wave transmitter to form a caseless tire pressure sensor. be able to. Moreover, a pressure sensor and a radio wave transmitter can be embedded in the curable resin composition for casting of the present invention and cured to form a caseless tire pressure sensor. Among these, from the viewpoint of impact resistance, mechanical strength, and circuit protection, it is preferable to embed a pressure sensor and a radio wave transmitter in the curable resin composition for casting of the present invention and cure.

  The curing temperature in the mold is preferably 20 to 100 ° C. A mold release agent can be applied to the mold in advance.

In the caseless tire air pressure sensor of the present invention, one of preferable embodiments is one in which a cured product obtained from the casting curable resin composition of the present invention has a higher hardness. In such a case, a hardened product with high hardness can serve as a case.
From the viewpoint of impact resistance, the cured product obtained by curing the curable resin composition for casting used in the caseless tire pressure sensor of the present invention has a hardness of 60 or more in JIS A hardness. preferable. Moreover, from the viewpoint of impact resistance and mechanical strength, the hardness after curing is preferably 80 or more, and more preferably 85 to 100. In such a range, the caseless tire air pressure sensor is less likely to be damaged by an impact during the manufacture of the tire or when the tire is incorporated into a vehicle. The measuring method of JIS A hardness is the same as the above.
The weight of the caseless tire pressure sensor of the present invention is preferably 30 g or less per piece.

The caseless tire pressure sensor of the present invention will be described with reference to the accompanying drawings. The caseless tire pressure of the present invention is not limited to the attached drawings.
FIG. 8 is a perspective view schematically showing an internal structure of a tire by cutting out a part of a tire having a tire wheel to which a caseless tire pressure sensor of the present invention is attached. In FIG. 8, 1 is a tire, 2 is a tire wheel, 3 is a rim, 4 is a rim flange, and 15 is a caseless tire pressure sensor.
The surface of the caseless tire pressure sensor 15 is a cured product of the casting curable resin composition of the present invention, and a battery (not shown), a pressure sensor, and a radio wave transmitter are incorporated therein. A base (not shown) is embedded. The caseless tire pressure sensor 15 is provided with a small communication hole 9 so that the pressure in the tire 1 can be detected by a pressure sensor (not shown). Since the caseless tire pressure sensor 15 does not use a case, the caseless tire pressure sensor 15 is not divided into upper and lower portions like the cased tire pressure sensor of FIGS.
The caseless tire pressure sensor 15 is attached to a part of the surface of the rim 3 via an adhesive means (not shown) such as an adhesive or a double-sided adhesive tape.

  EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

1. Preparation of glass balloon 1 Add 100 parts by mass of n-hexyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) to 100 parts by mass of glass balloon (manufactured by Fuji Silysia Chemical Co., Ltd., Fuji Balloon H-40). Then, the reaction was carried out for 24 hours while distilling off the produced methanol to obtain a glass balloon having an n-hexyl group bonded to the surface.

2. Evaluation method About the curable resin composition for casting of each Example shown in Table 1, dispersibility, viscosity, mixing property, specific gravity of cured product, and curing time were evaluated according to the following evaluation methods. The results are shown in Table 1. In addition, the unit of the compounding quantity of each component shown in Table 1 is a mass part.
2-1. Dispersibility About each of A liquid, B liquid, and the liquid mixture of A liquid and B liquid, the dispersibility of each liquid 1 hour after mixing | blending was confirmed visually.
The case where the glass balloon floats and separates in the upper layer of the liquid or the case where the glass balloon separates as a layer in the liquid is marked as x, and the glass balloon is uniformly dispersed and / or mixed in the liquid. The case where it has been evaluated as ○.

2-2. Viscosity Viscosity of each of liquid A, liquid B and liquid mixture of liquid A and liquid B was measured under the conditions of 20 ° C. using an E-type viscometer.

2-3. Mixability Liquid A and liquid B were mixed with a static mixer in the formulation shown in Table 1.
The case where the A liquid and the B liquid were uniformly mixed was evaluated as ◯, and the case where the A liquid and the B liquid were not mixed uniformly and curing did not occur uniformly was evaluated as x.

2-4. Specific gravity of cured product After curing 1 g of each curable resin composition for casting under the conditions of 20 ° C. and 65% RH for 24 hours, the specific gravity of the obtained cured product was changed under the condition of 25 ° C. by an underwater substitution method. Measured in
2-5. Curing time The curable resin composition for casting is placed in a 6 cm long and 2.5 cm wide container so that the height is 1 cm, and the time until curing under the conditions of 23 ° C. and 65% RH is the curing temperature. And measured.

3. Casting Curable Resin Composition Each component shown in Table 1 was mixed in the amount shown in Table 1 (unit is part by mass) to prepare each casting curable resin composition.

The details of each component in Table 1 are as follows.
-Silicone resin 1: ELASTOSIL RT601A, manufactured by Asahi Kasei Wacker Silicone-Silicone resin 2: ELASTOSIL RT604A, manufactured by Asahi Kasei Wacker Silicone-Silicone resin 3: ELASTOSIL RT745SA, manufactured by Asahi Kasei Wacker Silicone-Curing agent 1: ELASTOSIL RT601B, Asahi Kasei Wacker Silicone Co., Ltd./Curing agent 2: ELASTOSIL RT604B, Asahi Kasei Wacker Silicone Co., Ltd./Curing agent 3: ELASTOSIL RT745SB, Asahi Kasei Wacker Silicone Co., Ltd./Glass balloon 1: Glass balloon prepared as described above: Glass balloon 2: Fuji balloon H-40 Manufactured by Fuji Silysia Chemical Ltd.

4). Production of Caseless Tire Air Pressure Sensor A caseless tire air pressure sensor was produced using the curable resin composition for casting shown in Table 2 as follows.
First, a base (3 g per piece) and a battery (6.5 g per piece) with a pressure sensor and radio wave transmitter built in are set in the mold, the mold is closed, and a curable resin for casting is used. The composition was injected. After completing the injection, the mold was cured for 10 minutes under the condition of a mold temperature of 20 ° C., and the caseless tire pressure sensor was taken out of the mold. Table 2 shows the weight of the obtained caseless tire pressure sensor.

5. Evaluation of Caseless Tire Pressure Sensor The obtained caseless tire pressure sensor was measured and evaluated for JIS A hardness and impact resistance by the following methods. The results are shown in Table 2.
5-1. JIS A hardness According to JIS K6253-1997, the JIS A hardness of the caseless tire pressure sensor was measured.
5-2. Impact Resistance In accordance with JIS K7110-1997, an Izod impact tester was used, and an impact resistance test was performed in which an impact energy of 1 kgf · cm was applied to a caseless tire air pressure sensor as a test body using the Izod impact tester.
After the test, the test specimen was evaluated as “◯” when no crack was observed, and “X” when the crack was observed.

In addition, also about Example 7 of Table 2, and Comparative Examples 6-8, dispersibility, a viscosity, mixing property, and specific gravity of hardened | cured material were evaluated by the method similar to the above. The results are shown in Table 2.

The details of each component in Table 2 are as follows.
Polyisocyanate: Crude MDI (PAPI135, manufactured by Dow Chemical Japan Co., Ltd., a mixture containing two or more compounds represented by formula (3). Average value of n = 2.7)

Curing agent 4: 40 parts by mass of N, N′-tetra (2-hydroxypropyl) ethylenediamine (EDP-300, manufactured by Asahi Denka), 40 parts by mass of triethylene glycol, and polybutadiene polyol (R45HT, manufactured by Idemitsu Kosan Co., Ltd.) ) Mixture with 20 parts by mass / Curing catalyst 1: Tetravalent tin compound (trade name No918, manufactured by Sansha Co., Ltd.)
Curing catalyst 2: 1,4-diazabicyclo [2.2.2] octane, manufactured by Wako Pure Chemical Industries, Ltd. Glass balloon 1: Glass balloon prepared as described above Glass balloon 2: Fuji balloon H-40, Fuji Silysia Chemical Made by company

As is clear from the results shown in Tables 1 and 2, the curable resin compositions for casting of Examples 1 to 7 are excellent in dispersibility. On the other hand, Comparative Example 5 and Comparative Example 7 using a glass balloon that has not been surface-treated have low dispersibility in all of the liquid A, liquid B, and the liquid mixture of liquid A and liquid B.
Moreover, in the curable resin composition for casting of Examples 1-7, the viscosity of A liquid, B liquid, and these liquid mixtures is low. The casting curable resin compositions of Examples 1 to 7 are expected to increase in viscosity because the affinity between the chain saturated hydrocarbon group-containing glass balloon and the curable resin is increased. However, contrary to expectations, the viscosity could be kept low. On the other hand, Comparative Example 4 and Comparative Example 8 have a high viscosity and are inferior in fluidity and workability because the amount of the chain saturated hydrocarbon group-containing glass balloon is too large.
Furthermore, since the liquid mixture of A liquid and B liquid has low viscosity, it turns out that the curable resin composition for casting of this invention is hard to gelatinize. This is because the chain saturated hydrocarbon group-containing glass balloon does not have a functional group at the end of the chain saturated hydrocarbon group, and such end does not react with the curable resin, the curing agent and the curing catalyst. Guess.
The cured products obtained from the curable resin compositions for casting of Examples 1 to 7 have a low specific gravity and are lightweight.
Since the curable resin compositions for casting of Examples 1 to 7 include the chain saturated hydrocarbon group-containing glass balloons in both the liquid A and the liquid B, the mixing ability of the liquid A and the liquid B is excellent.

  As is apparent from the results shown in Table 2, the cured product obtained from the casting curable resin composition of Example 7 is excellent in hardness and impact resistance. On the other hand, Comparative Example 8 is inferior in impact resistance because the amount of the chain saturated hydrocarbon group-containing glass balloon is too large. Since Comparative Example 6 does not include the chain saturated hydrocarbon group-containing glass balloon, the hardness is low.

FIG. 1 is a perspective view from the top side schematically showing the external appearance of a cased tire pressure sensor of the present invention. FIG. 2 is a perspective view from the bottom side schematically showing the external appearance of the cased tire pressure sensor of the present invention. FIG. 3 is a side view schematically showing a side surface of the cased tire pressure sensor viewed from the direction of the arrow in FIG. 1. FIG. 4 is a plan view schematically showing the appearance of the cased tire pressure sensor of the present invention. FIG. 5 is a plan view schematically showing the internal structure of the cased tire pressure sensor of the present invention. FIG. 6 is a cross-sectional view of the cased tire pressure sensor 5 of FIG. 7 is a cross-sectional view of the cased tire pressure sensor 5 of FIG. 5 taken along the line BB. FIG. 8 is a perspective view schematically showing an internal structure of a tire by cutting out a part of a tire having a tire wheel to which a caseless tire pressure sensor of the present invention is attached.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Tire 2 Tire wheel 3 Rim 4 Rim flange 5 Cased tire pressure sensor 6a Cover side case 6b Base side case 6x Bottom face of the attachment part of the longitudinal direction of the base side case 6b 6y Chamfered part of the width direction of the tire pressure sensor 5 with the case 7 Battery 8 Base 9 Communication hole 9a Support member 9b Support member 10 Connection screw 11 Projection 13 Region 15 Caseless tire pressure sensor

Claims (9)

A curable resin composition for casting having a main agent containing a curable resin and an additive containing a curing agent and / or a curing catalyst,
At least one of the main agent and the additive includes a chain saturated hydrocarbon group-containing glass balloon that can be obtained by reacting a glass balloon and a silicon atom-containing compound represented by the following formula (1):
The amount of the chain saturated hydrocarbon group-containing glass balloon is 1 to 30 parts by mass with respect to a total of 100 parts by mass of the curable resin and the curing agent and / or curing catalyst. object.
(R ¹ O) _m -Si-R ² _4-m (1)
(In the formula, each R ¹ independently represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and each R ² independently represents a monovalent trivalent atom having 3 or more carbon atoms which may contain a hetero atom. Represents a chain saturated hydrocarbon group, the heteroatom does not exist at the terminal of the chain saturated hydrocarbon group, and m is an integer of 1 to 3).   The curable resin composition for casting according to claim 1, wherein the chain-saturated hydrocarbon group-containing glass balloon is contained in both the main agent and the additive.   The curable resin composition for casting according to claim 1 or 2, wherein the hardness after curing is 60 or more in terms of JIS A hardness.   The curable resin composition for casting according to any one of claims 1 to 3, wherein the curable resin is a reactive polyorganosiloxane, an epoxy resin, a polyisocyanate, or an olefin compound. The curable resin composition for casting according to any one of 1 to 4, wherein the amount of the silicon atom-containing compound used is 10 to 1,000 parts by mass with respect to 100 parts by mass of the glass balloon. The curable resin composition for casting according to any one of claims 1 to 5, which is used when producing an air pressure sensor. A tire-in-case tire pressure sensor that can be obtained by injecting and curing the curable resin composition for casting according to any one of claims 1 to 6 in a case in which a pressure sensor and a radio wave transmitter are arranged. A caseless that can be obtained by injecting and curing the curable resin composition for casting according to any one of claims 1 to 6 into a mold in which a pressure sensor and a radio wave transmitter are arranged, and taking out from the mold. Tire pressure sensor. The caseless tire pressure sensor according to claim 8 , wherein the curable resin is polyisocyanate.

Images