JP2013129754A - Method for manufacturing display device, and electric and electronic equipment, motorcycle and automobile each mounted with the display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a display device superior in visibility, workability and production efficiency, and electric and electronic equipment, a motorcycle and an automobile each mounted with the same.SOLUTION: The method for manufacturing the display device including a resin layer formed between a first member and a second member includes three steps of: (1) making a liquid curable composition into a gelatinous material by active energy ray curing and/or ordinary temperature curing; (2) mutually sticking the first member and the second member with the gelatinous material being in between; and (3) perfectly curing the gelatinous material by ordinary temperature curing and/or active energy ray curing.

Description

  In the present invention, the space between the first member and the second member is filled with a gel-like material that has been cured in advance at room temperature and / or with active energy rays, followed by active energy curing and / or room temperature curing. The present invention relates to a manufacturing method of a display device that is completely cured, and an electric / electronic device, a motorcycle, and an automobile on which they are mounted.

  For conventional mobile phones and smartphone touch panels, when bonding between cover boards / touch panels or between touch panels / liquid crystal modules, etc., even if there is a step in the electrode part, etc. Even when the coating amount is increased, there is a concern of peeling from the vicinity of the electrode portion, poor adhesion, and mixing of bubbles due to the fact that the film thickness cannot be thicker than 500 μm due to liquid flow-out.

  Furthermore, for the liquid resin filling between the cover glass and the module for the purpose of improving the visibility and impact resistance of the large screen of PDP (plasma display panel) and liquid crystal TV, the size of the cover glass is as large as 40 inches or more. Therefore, it may be necessary to have a film thickness of 500 μm or more. However, for the same reason as above, it is difficult to ensure the thickness of the resin layer, and the bending due to the weight of the cover glass and the module. Therefore, it is difficult to keep the film thickness uniform.

  In addition, in resin filling applications for the purpose of improving the visibility of instrument panel parts of motorcycles and automobiles, the coating part is not flat, and it is difficult to ensure a uniform thickness when applied in a liquid state. However, it is necessary to attach a display pointer after the resin layer is cured. In the case of the UV single curing system, there is a problem that it is difficult to balance the flexibility and strength of the resin when the needle is inserted through the resin after curing. It was.

  The above-mentioned problem has not been solved yet by a bonding resin that is applied in a liquid state and cured by UV.

JP 2011-208072 A

  In order to improve the visibility and impact resistance of a display device such as a liquid crystal touch panel, an organic EL touch panel, a liquid crystal module, and a PDP, the present invention provides an air gap portion (e.g., between module / cover board, module / backlight). Display devices such as liquid crystal touch panels, organic EL touch panels, liquid crystal modules, PDPs, digital and analog speedometers with short manufacturing time and excellent adhesion durability and processability Manufacturing methods, and electric / electronic devices / motorcycles and automobiles equipped with them.

  In order to improve the visibility and impact resistance of display devices such as liquid crystal touch panels, organic EL touch panels, liquid crystal modules, and PDPs, when filling the air gap with resin, it is not applied in a liquid state. , Liquid resin is pre-cured with active energy rays or gel material cured at room temperature, and then cured completely at room temperature or with active energy rays. The present inventors have found a method for manufacturing a display device that is excellent in workability such as the property.

That is, the present invention relates to a method for manufacturing a display device in which a resin layer is formed between a first member and a second member, and relates to a method for manufacturing a display device through the following three steps.
(1) The process which makes a liquid curable composition a gel-like material by active energy ray hardening and / or normal temperature hardening.
(2) The process of bonding so that a gel-like thing may be inserted | pinched between a 1st member and a 2nd member.
(3) A step of completely curing the gel-like material by normal temperature curing and / or active energy ray curing.

  In the step (2), after the gel material and the first member are bonded together, the parts are attached to the surface of the gel material or the first substrate, and then the gel material and the second member are attached. It is preferable to bond them together.

  It is preferable that room temperature curing is moisture curing.

  The active energy ray is preferably selected from EB (electron beam) and UV, and more preferably UV.

  The liquid curable composition (A) having an average of at least one polymerizable carbon-carbon double bond in one molecule and a compound having an average of at least one hydrolyzable silyl group in one molecule ( B) is preferably included.

  The liquid curable composition preferably contains a polymerization initiator (C).

  The polymerization initiator (C) is preferably selected from at least one of a photopolymerization initiator and a redox initiator, and more preferably a photopolymerization initiator.

  The liquid curable composition preferably contains a curing catalyst (D).

  The curing catalyst (D) is preferably selected from at least one of an organic metal, an acid catalyst, and an acid / base catalyst, and at least one selected from an organic tin catalyst, a phosphoric acid catalyst, and a phosphoric acid / amine catalyst. It is more preferable.

  It is preferable that the component (A) and / or the component (B) is at least one selected from polysiloxane, polyether, and vinyl polymer, polyoxyethylene, polyoxypropylene, polyisobutylene, hydrogenated Produced mainly by polymerizing polyisoprene, hydrogenated polybutadiene, and monomers selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. More preferably, it is at least one selected from polymers to be prepared, and more preferably at least one selected from polyoxyethylene, polyoxypropylene, polyisobutylene, and (meth) acrylic polymers.

  The component (A) and / or the component (B) is preferably a (meth) acrylic polymer, more preferably an acrylic polymer, and even more preferably an acrylic ester polymer.

The polymerizable carbon-carbon double bond of the component (A) has the general formula (1)
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
It is preferable that it is group represented by these.

It is preferable that the hydrolyzable silyl group of (B) component is represented by General formula (101).
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (101)
(In the formula, R ¹ and R ² are the same or different and each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO. (In the formula, R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. The plurality of R ′ may be the same or different. When two or more R ¹ or R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and two or more Y are present. , They may be the same or different, a represents 0, 1, 2, or 3. b represents 0, 1, or 2. m represents an integer of 0 to 19. A + mb ≧ 1)

  (A) It is preferable that the number average molecular weight of a component is 5000 or more.

  It is preferable to further contain a monomer and / or oligomer (E) having a (meth) acryloyl group and having a number average molecular weight of 5000 or less.

  The molecular weight distribution of the components (A) and (B) is preferably less than 1.8.

  It is preferable that the main chains of the components (A) and (B) are produced by a living polymerization method.

  It is preferable that the polymerizable carbon-carbon double bond of component (A) and / or the hydrolyzable silyl group of component (B) are at the molecular chain terminal.

  The display device is preferably a liquid crystal touch panel, an organic EL touch panel, a liquid crystal module, a PDP, a digital and an analog speedometer.

  Electric / electronic devices, motorcycles, automobiles equipped with the display device obtained by the above manufacturing method.

  In order to improve the visibility and impact resistance of a display device such as a liquid crystal touch panel, an organic EL touch panel, a liquid crystal module, and a PDP, the present invention can provide an air gap (for example, between a module and a cover board, between a module and a backlight). Of air gap, etc.) When a part is filled with resin, a manufacturing method of a display device with a short manufacturing time, excellent adhesion durability and workability is provided, and an electric / electronic device / motorcycle and automobile equipped with them are provided. .

The present invention is a method for manufacturing a display device in which a resin layer is formed between a first member and a second member, and is a method for manufacturing a display device through the following three steps.
(1) The process which makes a liquid curable composition a gel-like material by active energy ray hardening and / or normal temperature hardening.
(2) The process of bonding so that a gel-like thing may be inserted | pinched between a 1st member and a 2nd member.
(3) A step of completely curing the gel-like material by normal temperature curing and / or active energy ray curing.

  In the present invention, the liquid curable composition is first made into a gel-like material. The gel-like material means a state in which the crosslinkable reactive group is not completely reacted, although it does not flow.

<< Display Device Manufacturing Method >>
In the present invention, two types of curing methods are sequentially performed: curing for obtaining a gel-like material and subsequent complete curing.

  Curing to obtain a gel-like material and subsequent curing method can use either active energy ray curing, room temperature curing, or both. Curing to obtain a gel-like material and subsequent complete curing May be the same curing method or different curing methods.

  As the curing method of the present invention, moisture curing is used as a method for obtaining a gel-like material, and active energy ray curing is preferably used for complete curing in terms of curability and stability at the time of liquefaction.

  Examples of curing with active energy rays include UV and EB (electron beam) rays, but UV curing is preferred.

  In the case of curing by irradiating light or electron beam with an active energy ray source, the active energy ray source is not particularly limited, but depending on the properties of the photopolymerization initiator used, for example, a high pressure mercury lamp, a low pressure mercury lamp, an electron beam. Irradiation devices, halogen lamps, light emitting diodes, semiconductor lasers, metal halides and the like can be mentioned.

  Examples of room temperature curing include moisture curing and Redx curing, but moisture curing is preferred.

  When curing by moisture curing, the relative humidity is preferably 5 to 95%, more preferably 10 to 80%.

<Step (1)>
The step (1) is a step in which the liquid curable composition is made into a gel by active energy ray curing and / or room temperature curing.

  As a method for obtaining a gel-like material, a kind of curing method is selected from active energy ray curing and / or room temperature curing, and a substrate such as polyolefin, PET, PMMA, polycarbonate, cycloolefin, polyimide (the shape is a plate, A method in which a liquid resin is applied with a specific thickness to a gel shape is preferable, although it is not particularly limited. Although not limited, in general, the gel-like cured product formed on the substrate is preferably sanded with the substrate or release paper in consideration of convenience in handling.

  The curing method for obtaining the gel-like material may be either active energy ray curing, room temperature curing, or both.

  In the case of active energy ray curing, by controlling the irradiation intensity and the amount of accumulated energy, even if the active energy ray is irradiated, it only becomes a gel, and complete curing does not occur.

When the active energy ray is UV irradiation, the UV irradiation amount is preferably 50 to 2000 mJ / cm ^2, more preferably 100 to 1000 mJ / cm ² .

  In the case of room temperature curing, by controlling the curing time under a certain range of temperature and humidity conditions, it only becomes a gel and does not completely cure.

  In the case of room temperature curing, the temperature condition is 10 to 40 ° C., the humidity range is 10 to 80%, the curing period, and the curability is controlled by the curing time, preferably 6 to 72 hours. Furthermore, it is preferably 12 to 24 hours. In order to stop the progress of curability, it is preferable to seal with a plastic or glass film after curing.

  The reaction rate of the gel is preferably 10 to 90%, more preferably 30 to 80%, and still more preferably 50 to 70%.

<Step (2)>
The step (2) is a step of bonding the gel-like material obtained in the step (1) so as to be sandwiched between the first member and the second member.

  The method for bonding the first member and the second member is not particularly limited, but the gel coated and cured on the substrate is bonded to the first member together with the substrate, and the substrate is removed. A method in which the second member is pasted after is preferred.

  As the first member and the second member, any member can be used as long as it is used for a display device such as a liquid crystal touch panel, an organic EL touch panel, a liquid crystal module, and a PDP, but it is necessary to fill with a resin. From the viewpoint of having an air gap portion, a combination of a display module and a cover board, a display module and a backlight, a protective cover and a speed meter, a touch panel (touch sensor) and a protective cover is preferable. One member of the combination is the first member and the other member is the second member, but the first member and the second member are not limited to either member.

  In the step (2), after bonding the gel-like material to the first member, the part may be attached to the surface of the gel-like material or the first substrate, and then the second member may be attached. .

  For example, in the case of an analog type meter, a gel-like material may be bonded to the meter display portion, and then boring and attaching a pointer to the gel-like material may be performed. When the cured product is completely cured, the cured product may be destroyed when the cured product is bored or cut. Therefore, it is preferable to attach the component in a gel-like product that is not completely cured.

<Step (3)>
The step (3) is a step of completely curing the gel-like material by normal temperature curing and / or active energy ray curing.

  The curing method for complete curing may be active energy ray curing, room temperature curing, or both.

  Since it is preferable to adopt another curing method for the curing method for obtaining the gelled product and the complete curing, when the active energy ray curing is employed for the curing method for obtaining the gelled product, the complete curing method is a room temperature curing. preferable. Moreover, when normal temperature hardening is employ | adopted as the hardening method which obtains a gelled material, active energy ray hardening is preferable for the complete hardening method.

When active energy ray curing is employed for complete curing, the curing condition is preferably UV curing. The accumulated light amount is preferably 2000 to 50000 mJ / cm ^2, more preferably 2500 to 30000 mJ / cm ² .

  When room temperature curing is adopted for complete curing, the curing conditions are room temperature curing, the temperature condition is preferably 10 to 40 ° C., and the humidity range is preferably 10 to 80%, and the curability is controlled by the curing time. 72 hours to 2 weeks is preferred, and 72 hours to 1 week is more preferred.

<< Liquid curable composition >>
The liquid curable composition of the present invention may be any one as long as it is cured by active energy ray curing and / or room temperature curing, but averages a polymerizable carbon-carbon double bond in one molecule. The compound (A) having at least one and the compound (B) having at least one hydrolyzable silyl group on average in one molecule are preferably included.

<(A) component and (B) component>
The skeletons of the component (A) and the component (B) may be the same or different, but are preferably the same skeleton from the viewpoint of compatibility. In addition, the component (A) and the component (B) may be any of a low molecular weight compound, an oligomer, and a polymer, but are oligomers or organic in terms of a balance of flexibility, durability, and curability. A polymer is preferred, and an organic polymer is particularly preferred.

  The organic polymer refers to a compound having a repeating unit of an organic compound and comprising 100 or more repeating units. An oligomer refers to a compound having a repeating unit of an organic compound and comprising 2 to 100 repeating units. The low molecular weight compound is a compound having a structure other than an oligomer or an organic polymer and basically having no repeating unit.

  As the organic polymer or oligomer, polysiloxane, polyether, or vinyl polymer is preferable.

  As the polysiloxane, alkyl polysiloxane is preferable.

  The polyether is preferably an oxyalkylene polymer, and more preferably polyoxyethylene or polyoxypropylene.

  Examples of the vinyl polymer include hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, and fluorine-containing vinyls. A polymer produced mainly by polymerizing a monomer selected from the group consisting of a system monomer and a silicon-containing vinyl monomer is preferred. Here, “mainly” means that 50 mol% or more of the monomer units constituting the vinyl polymer is the above monomer, and preferably 70 mol% or more. Furthermore, the vinyl polymer is preferably a (meth) acrylic polymer produced mainly by polymerizing polyisobutylene and a (meth) acrylic monomer, more preferably an acrylic polymer, and a polymerized acrylate monomer. An acrylic ester polymer produced by the above method is more preferable.

  (Meth) acrylic monomers include: (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid n-butyl, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid n-heptyl, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, Isodecyl (meth) acrylate, isobornyl (meth) acrylate, disishi (meth) acrylate Lopentanyl, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, (Meth) acrylate 2-hydroxyethyl, (meth) acrylate 2-hydroxypropyl, stearyl (meth) acrylate, isostearyl (meth) acrylate, glycidyl (meth) acrylate, 2-amino (meth) acrylate Ethyl, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth) acrylic 2-perfluoroethylethyl acid, (meth) a 2-perfluoroethyl-2-perfluorobutylethyl acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, (meth) acrylic acid 2-perfluoromethyl-2-perfluoroethylethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate, etc. (Meth) acrylic acid ester monomers and the like.

  Examples of acrylonitrile monomers include acrylonitrile and methacrylonitrile.

  Examples of the aromatic vinyl monomer include styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and salts thereof.

  Examples of the fluorine-containing vinyl monomer include perfluoroethylene, perfluoropropylene, and vinylidene fluoride.

  Examples of the silicon-containing vinyl monomer include vinyltrimethoxysilane and vinyltriethoxysilane.

  The molecular weight distribution of the organic polymer or oligomer of component (A) and / or the organic polymer or oligomer of component (B), that is, the weight average molecular weight (Mw) and number measured by gel permeation chromatography (GPC). The ratio (Mw / Mn) of the average molecular weight (Mn) is not particularly limited, but is preferably less than 1.8, more preferably 1.7 or less, further preferably 1.6 or less, and further Preferably it is 1.5 or less, Especially preferably, it is 1.4 or less, Most preferably, it is 1.3 or less. When the molecular weight distribution is 1.8 or more, the viscosity increases and the handling tends to be difficult. In addition, GPC measurement in this invention uses chloroform as a mobile phase, a measurement is performed with a polystyrene gel column, and a number average molecular weight etc. can be calculated | required by polystyrene conversion.

  Since any oligomer and organic polymer can be explained in common with respect to the main chain, the production method, etc., they will be explained together below.

[Polysiloxane]
Known methods for producing organopolysiloxanes by hydrolyzing organochlorosilane, Japanese Patent No. 2599517, Japanese Patent Laid-Open No. 56-151731, Japanese Patent Laid-Open No. 59-66422, Japanese Patent Laid-Open No. 59-68377 Can be obtained by a known method such as a hydrolysis method in the presence of a basic catalyst or an acid catalyst. Examples of the terminal functional group of the polymer include an alkoxysilyl group, a silanol group, and a hydroxyl group.

  The number average molecular weight of the polysiloxane in the present invention is not particularly limited, but is 500 to 1,000,000, more preferably 3,000 to 100,000, when measured by GPC. If the molecular weight is too low, the elongation and flexibility tend to be insufficient, and if it is too high, the viscosity tends to increase and workability such as coating tends to decrease.

[Polyether]
The method for synthesizing the polyether (oxyalkylene polymer) is not particularly limited. For example, it can be obtained by ring-opening polymerization of a monoepoxide in the presence of an initiator and a catalyst.

  Specific examples of the initiator include ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, methallyl alcohol, bisphenol A, hydrogenated bisphenol A, neopentyl glycol, polybutadiene diol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene Examples thereof include dihydric alcohols such as glycol, polypropylene triol, polypropylene tetraol, dipropylene glycol, glycerin, trimethylol methane, trimethylol propane, and pentaerythritol, polyhydric alcohols, and various oligomers having a hydroxyl group.

  Specific examples of the monoepoxide include ethylene oxide, propylene oxide, α-butylene oxide, β-butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide, α-methylstyrene oxide, and other alkylene oxides, methyl glycidyl ether, ethyl Examples thereof include alkyl glycidyl ethers such as glycidyl ether, isopropyl glycidyl ether, and butyl glycidyl ether, allyl glycidyl ethers, and aryl glycidyl ethers.

  As a polymerization method, a polymerization method using an alkali catalyst such as KOH, or a transition metal compound-porphyrin complex catalyst such as a complex obtained by reacting an organoaluminum compound and porphyrin described in JP-A-61-215623 is used. Examples of the polymerization method include a polymerization method using a double metal cyanide complex catalyst, a polymerization method using a cesium catalyst, a polymerization method using a phosphazene catalyst, etc., as disclosed in Japanese Patent Publication Nos. 46-27250 and 59-15336. It is not limited. Among these, a polymerization method using a double metal cyanide complex catalyst is preferable from the viewpoint of easily obtaining a polymer having a high molecular weight and little coloring.

In addition, the main chain skeleton of the oxyalkylene polymer is a hydroxyl group-terminated oxyalkylene polymer in the presence of a basic compound such as KOH, NaOH, KOCH ₃ , NaOCH ₃ or the like, and a bifunctional or higher alkyl halide such as CH can also be obtained by chain extension due ₂ Cl _{2, CH 2} Br ₂ or the like.

  Further, the main chain skeleton of the oxyalkylene polymer may contain other components such as a urethane bond component as long as the characteristics of the oxyalkylene polymer are not significantly impaired.

  The number average molecular weight of the polyether in the present invention is not particularly limited, but is 500 to 1,000,000, more preferably 1,000 to 100,000 when measured by GPC. If the molecular weight is too low, the elongation and flexibility tend to be insufficient, and if it is too high, the viscosity tends to increase and workability such as coating tends to decrease.

[Vinyl polymer]
(Hydrocarbon polymer)
The hydrocarbon polymer is a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring. For example, 1,2-polybutadiene, 1,4-polybutadiene, polyethylene, polypropylene, polyisobutylene , Hydrogenated polybutadiene, hydrogenated polyisoprene, and the like.

  The polymer constituting the main chain skeleton of the hydrocarbon polymer used in the present invention is (1) carbon number 1 such as ethylene, propylene, 1,2-butadiene, 1,4-butadiene, 1-butene, isobutylene and the like. The olefinic compound of -6 is homopolymerized or copolymerized as a main component, or (2) a diene compound such as butadiene or isoprene is homopolymerized or copolymerized, or the olefinic compound is copolymerized. Thereafter, it can be obtained by a method such as hydrogenation.

  Among these, polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene are preferable because it is easy to introduce a functional group at the terminal, easily control the molecular weight, and increase the number of terminal functional groups. Furthermore, since polyisobutylene has liquid or fluidity, it is easy to handle, and since it does not contain any carbon-carbon unsaturated bonds other than aromatic rings in the main chain, there is no need for hydrogenation and it is particularly excellent in weather resistance. preferable. In the polyisobutylene, all of the monomer units may be formed from isobutylene units, or the monomer units copolymerizable with isobutylene are preferably 50 wt% or less, more preferably 30 wt% in polyisobutylene. % Or less, particularly preferably 10% by weight or less.

  Examples of such monomer components for hydrocarbon polymerization include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, and allyl silanes. For example, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene , Α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane , Divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, allyltrichlorosilane, allyl Examples include methyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallyldimethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropylmethyldimethoxysilane. .

  In the hydrogenated polyisoprene, hydrogenated polybutadiene, and other hydrocarbon polymers, as in the case of the above polyisobutylene, other monomer units may be contained in addition to the main monomer unit. Good.

  The number average molecular weight of the hydrocarbon polymer, preferably polyisobutylene, hydrogenated polyisoprene, or hydrogenated polybutadiene is preferably about 500 to 50,000, and particularly liquid or fluidity of about 1,000 to 20,000. It is preferable from the viewpoint of easy handling.

(Vinyl polymers other than hydrocarbon polymers)
The vinyl polymer other than the hydrocarbon polymer in the present invention is not particularly limited as the vinyl monomer constituting the main chain, and various types can be used. Specifically, (meth) acrylic acid monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, silicon-containing vinyl monomers, maleimides such as various monomers described in paragraph [0018] of JP-A-2005-232419 Examples thereof include vinyl monomers, nitrile group-containing vinyl monomers, amide group-containing vinyl monomers, vinyl esters, alkenes, conjugated dienes, vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. These may be used alone or a plurality of these may be copolymerized. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  The main chain of the vinyl polymer other than the hydrocarbon polymer used in the curable composition of the present invention is a (meth) acrylic monomer, an acrylonitrile monomer, an aromatic vinyl monomer, a fluorine-containing vinyl monomer, and It is preferable that it is produced mainly by polymerizing at least one monomer selected from the group consisting of silicon-containing vinyl monomers. Here, “mainly” means that 50 mol% or more of the monomer units constituting the vinyl polymer (b) is the above monomer, and preferably 70 mol% or more.

  Of these, aromatic vinyl monomers and / or (meth) acrylic acid monomers are preferred, acrylic acid ester monomers and / or methacrylic acid ester monomers are more preferred, and acrylic acid ester monomers are even more preferred from the physical properties of the product. . Particularly preferred acrylic ester monomers include alkyl acrylate monomers, specifically ethyl acrylate, 2-methoxyethyl acrylate, stearyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic acid. 2-methoxybutyl. In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in this case, these preferred monomers may be contained in a weight ratio of 40% by weight or more. preferable.

  The number average molecular weight of the vinyl polymer other than the hydrocarbon polymer in the present invention is not particularly limited, but it is in the range of 500 to 1,000,000 when measured by GPC, 3,000 to 100,000. 000 is more preferred, 5,000 to 80,000 is more preferred, and 8,000 to 50,000 is even more preferred. If the molecular weight is too low, the original characteristics of vinyl polymers other than hydrocarbon polymers tend to be difficult to be expressed. On the other hand, if the molecular weight is too high, handling tends to be difficult.

  The vinyl polymer used in the present invention can be obtained by various polymerization methods, and is not particularly limited, but is preferably a radical polymerization method from the viewpoint of versatility of the monomer, ease of control, etc. Radical polymerization is more preferred. This controlled radical polymerization method can be classified into a “chain transfer agent method” and a “living radical polymerization method” which is a kind of living polymerization. Living radical polymerization, in which the molecular weight and molecular weight distribution of the resulting vinyl polymer can be easily controlled, is further preferred, and atom transfer radical polymerization is particularly preferred from the viewpoint of availability of raw materials and ease of introduction of a functional group at the polymer terminal. The above radical polymerization, controlled radical polymerization, chain transfer agent method, living radical polymerization method, and atom transfer radical polymerization are known polymerization methods. For example, JP-A-2005-232419 and Reference can be made to the description in Japanese Unexamined Patent Application Publication No. 2006-291073.

  Atom transfer radical polymerization, which is one of the preferred methods for synthesizing vinyl polymers other than hydrocarbon polymers in the present invention, will be briefly described below.

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

  In order to obtain a vinyl polymer having two or more alkenyl groups capable of hydrosilylation in one molecule, an organic halide having two or more starting points or a sulfonyl halide compound is used as an initiator. preferable. For example,

Etc.

  There is no restriction | limiting in particular as a vinyl-type monomer used in atom transfer radical polymerization, All the vinyl-type monomers mentioned above can be used conveniently.

  Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses a periodic table group 7, 8, 9, 10, or 11 element as a central metal, More preferably, it is 0. A transition metal complex having valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel as a central metal, particularly preferably a copper complex. Specific examples of the monovalent copper compound used to form the copper complex include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, and oxidized oxide. Cuprous, cuprous perchlorate, and the like. In the case of using a copper compound, 2,2′-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity These polyamines are added as ligands.

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

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

[Polymerizable carbon-carbon double bond introduction method (synthesis method of component (A))]
The polymerizable carbon-carbon double bond of the component (A) is not particularly limited, but the general formula (1)
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
The (meth) acryloyl group represented by these is preferable.
The polymerizable carbon-carbon double bond of component (A) is preferably at the end of the molecular chain.

(Introduction method to polysiloxane)
Although there is no particular limitation, for example, a hydrolyzable silyl group-containing vinyl compound, a hydrolyzable silyl group-containing (meth) acryloyl compound can be prepared by using an organometal or the like as a terminal silanol-terminated polysiloxane described in Japanese Patent No. 3193866. Examples include a method of hydrolytic condensation reaction.

(Introduction method to polyether)
The method for introducing a polymerizable carbon-carbon double bond into the oxyalkylene polymer is not particularly limited, but <1> a polyoxyalkylene having a hydroxyl terminal is reacted with an acid chloride compound of the general formula (1). <2> a method of reacting a compound of the general formula (1) containing an isocyanate group with a polyoxyalkylene having a hydroxyl terminal, <3> a polyfunctional isocyanate with a polyoxyalkylene having a hydroxyl terminal, and A method of reacting a vinyl monomer containing a hydroxyl group, <4> a polysilyl group having a hydrosilylation capable double bond terminal (for example, allyl group terminal) polyoxyalkylene, and a polyfunctional type hydrosilyl compound, and further reacting with allyl (meth) acrylate, etc. There is a method of reacting a compound capable of hydrosilylation. The methods <2>, <3>, and <4> are preferable from the viewpoint of the simplicity of the reaction, and the methods <2> and <3> are more preferable from the viewpoint of the stability of the reaction.

(Introduction method to vinyl polymer)
As a method for introducing a polymerizable carbon-carbon double bond into the vinyl polymer, a known method can be used. For example, the method described in paragraphs [0080] to [0091] of JP-A-2004-203932 can be mentioned, and the following method is preferable.

(Introduction method 1)
A method of replacing the terminal halogen group of the vinyl polymer of the general formula (2) with a compound having a polymerizable carbon-carbon double bond of the general formula (3).
-CR ^b R ^c X (2)
(In the formula, R ^b and R ^c are groups bonded to the ethylenically unsaturated group of the vinyl monomer. X represents chlorine, bromine or iodine.)
M ^{+ −} OC (O) C (R) ═CH ₂ (3)
(In the formula, R represents hydrogen or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal or a quaternary ammonium ion.)
The vinyl polymer having a terminal structure represented by the general formula (2) is a method of polymerizing a vinyl monomer using the above-described organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or Although it is produced by a method of polymerizing a vinyl monomer using a halogen compound as a chain transfer agent, the former is preferred.
Formula is not particularly restricted but includes compounds represented by (3), specific examples of R, for _{example, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n is It represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, etc., and is preferably -H, -CH _3. M ⁺ is a counter cation of an oxyanion, and examples of M ⁺ include alkali metal ions, specifically lithium ions, sodium ions, potassium ions, and quaternary ammonium ions. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, and dimethylpiperidinium ion, preferably sodium ion and potassium ion. The usage-amount of the oxyanion of General formula (3) becomes like this. Preferably it is 1-5 equivalent with respect to the halogen group of General formula (2), More preferably, it is 1.0-1.2 equivalent. The solvent for carrying out this reaction is not particularly limited but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric Triamide, acetonitrile, etc. are used. Although the temperature which performs reaction is not limited, Generally it is 0-150 degreeC, In order to hold | maintain a polymeric terminal group, Preferably it carries out at room temperature-100 degreeC.

(Introduction method 2)
A method of reacting a compound represented by the general formula (4) with a vinyl polymer having a hydroxyl group at the terminal. XC (O) C (R) = CH ₂ (4)
(In the formula, R represents hydrogen or an organic group having 1 to 20 carbon atoms. X represents chlorine, bromine, or a hydroxyl group.)

(Introduction method 3)
A method in which a diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at a terminal, and a residual isocyanate group is reacted with a compound represented by the following general formula 5.
HO—R′—OC (O) C (R) ═CH ₂ (5)
(In the formula, R represents hydrogen or an organic group having 1 to 20 carbon atoms. R ′ represents a divalent organic group having 2 to 20 carbon atoms.)

  Among these methods, (Introduction method 1) is most preferable because it is easy to control.

[Method for Introducing Crosslinkable Silyl Group (Method for Synthesizing Component (B))]
The hydrolyzable silyl group as used in the field of this invention is a silicon-containing functional group which can be bridge | crosslinked by forming a siloxane bond, and the group represented by General formula (101) is preferable.
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (101)
(In the formula, R ¹ and R ² are the same or different and each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO. (In the formula, R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. The plurality of R ′ may be the same or different. When two or more R ¹ or R ² are present, they may be the same or different.
Y represents a hydroxyl group or a hydrolyzable group. When two or more Y are present, they may be the same or different. a represents 0, 1, 2 or 3; b represents 0, 1, or 2. m shows the integer of 0-19. However, it is satisfied that a + mb ≧ 1. )
The hydrolyzable silyl group of component (B) is preferably at the end of the molecular chain.

(Introduction method to polysiloxane)
The method for introducing a hydrolyzable silyl group is not particularly limited. For example, when a polysiloxane is synthesized using a silane compound containing a hydrolyzable silyl group as an acid and a base as a catalyst component, the hydrolysis and condensation conditions are set. There are a method of adjusting and leaving hydrolyzable silyl at the terminal, a method of reacting a terminal chloro group-containing polysiloxane with chlorosilane containing hydrolyzable silyl, and the like.

(Introduction method to polyether)
(Α) A method of reacting a hydrosilyl compound represented by the general formula (102) after introducing an olefin group into an oxyalkylene polymer having a functional group such as a hydroxyl group.
HSiX _a R ² _3-a (102)
(Wherein R ² , X and a are the same as above)
Here, as a method for introducing an olefin group, a compound having both an unsaturated group and a functional group capable of reacting with a hydroxyl group is reacted with a hydroxyl group of an oxyalkylene polymer to form an ether bond, an ester bond, a urethane bond, and a carbonate bond. And a method of introducing an olefin group by adding and copolymerizing an olefin group-containing epoxy compound such as allyl glycidyl ether when the alkylene oxide is polymerized.

(Β) A method of reacting a compound represented by the general formula (103) with an oxyalkylene polymer having a functional group capable of reacting with an isocyanate compound.
_{^{(R 2 -) 3-a}} SiX a -R 3 NCO (103)
(In the formula, R ² , X and a are the same as above. R ³ is a divalent hydrocarbon group having 1 to 17 carbon atoms.)

(Γ) After an isocyanate group is introduced by reacting a polyisocyanate compound such as tolylene diisocyanate with an oxyalkylene polymer having a functional group capable of reacting with an isocyanate compound, the isocyanate group is represented by the general formula (104). A method of reacting a W group of a silicon compound.
^{_{(R 2 -) 3-a}} SiX a -R 3 W (104)
(Wherein R ² , R ³ , X, and a are the same as described above. W represents an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group, and an amino group (primary or secondary).)

(Δ) An olefin group is introduced into an oxyalkylene polymer having a functional group into which an olefin group can be introduced, and the olefin group is reacted with a silicon compound represented by the general formula (104) in which W is a mercapto group. Method.
Of these, the methods (α) and (β) are preferred from the introduction yield and the simplicity of the introduction method, and the method (α) is more preferred from the viewpoint of resin physical properties such as viscosity.

(Introduction method to vinyl polymer)
1) Hydrocarbon polymer There is no particular limitation, but introduction by the method (α) is preferable in terms of introduction yield and ease of reaction.

2) Vinyl-based polymers other than hydrocarbon-based methods The methods described in paragraphs [0102] to [0112] of JP-A-2004-210858 can be mentioned. Among these methods, it is produced by a method in which the alkenyl group of a polymer having a terminal alkenyl group is converted to a crosslinkable silyl group by a hydrosilylation reaction with a hydrosilane compound having a crosslinkable silyl group because it is easier to control. It is preferable that

<Polymerization initiator (C)>
When the curable composition of the present invention contains the component (A), it is not particularly limited, but the polymerization initiator (C) is used to cure quickly or to obtain a cured product having sufficient properties. Is preferred. The polymerization initiator (C) is not particularly limited, and examples thereof include a photopolymerization initiator for active energy ray curing and a redox initiator for room temperature curing. The photopolymerization initiator and the redox initiator may be used alone or as a mixture of two or more, but when used as a mixture, the amount of each initiator used is It is preferable that it exists in each range mentioned later.

  As a photoinitiator, a photoradical initiator, a photoanion initiator, a near-infrared photoinitiator, etc. are mentioned, A photoradical initiator and a photoanion initiator are preferable, and a photoradical initiator is particularly preferable.

Examples of the photo radical initiator include acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2, 2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4 -Chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin Tyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxy ketal, 2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl -Ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl- Examples include 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, dibenzoyl and the like.
Among these, α-hydroxy ketone compounds (for example, benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxy-cyclohexyl-phenyl-ketone, etc.), phenyl ketone derivatives (for example, acetophenone, propiophenone, benzophenone, 3-methyl) Acetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4-chloro-4′-benzylbenzophenone, bis (4-dimethylaminophenyl) ketone, etc.) are preferred.

  Examples of the photoanion initiator include 1,10-diaminodecane, 4,4′-trimethylenedipiperazine, carbamates and derivatives thereof, cobalt-amine complexes, aminooxyiminos, ammonium borates and the like. .

  As the near infrared photopolymerization initiator, a near infrared light absorbing cationic dye or the like may be used. As the near-infrared light absorbing cationic dye, near-infrared light which is excited by light energy in the region of 650 to 1500 nm, for example, disclosed in JP-A-3-111402, JP-A-5-194619, etc. An absorptive cationic dye-borate anion complex or the like is preferably used, and a boron sensitizer is more preferably used in combination.

  These photopolymerization initiators may be used alone or in combination of two or more, or may be used in combination with other compounds.

Specific examples of combinations with other compounds include combinations with amines such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, and combinations with iodonium salts such as diphenyliodonium chloride, methylene blue, and the like. Examples include those combined with a dye and an amine.
In addition, when using the said photoinitiator, polymerization inhibitors, such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, para tertiary butyl catechol, can also be added as needed.

  When using a photoinitiator, the addition amount does not have a restriction | limiting in particular, However, 0.001-10 weight part is preferable with respect to 100 weight part of (A) component from the point of sclerosis | hardenability and storage stability.

  Suitable redox initiators include, but are not limited to, a combination of a persulfate initiator and a reducing agent (sodium metabisulfite, sodium bisulfite, etc.); a combination of an organic peroxide and a tertiary amine For example, a combination of benzoyl peroxide and dimethylaniline, a combination of cumene hydroperoxide and anilines; a combination of organic peroxide and transition metal, for example, a combination of cumene hydroperoxide and cobalt naphthate, and the like.

  Persulfate initiators include, but are not limited to, potassium persulfate, sodium persulfate, ammonium persulfate, and the like.

  Examples of the organic peroxide include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydi. Carbonate (Perkadox 16S) (available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11) (available from Elf Atochem), t-butyl peroxy-2 -Ethylhexanoate (Trigonox 21-C50) (available from Akzo Nobel), cumene hydroperoxide, dicumyl peroxide and the like.

  Preferred redox initiators are a combination of organic peroxide and tertiary amine, a combination of organic peroxide and transition metal, and more preferably a combination of cumene hydroperoxide and anilines, cumene hydroperoxide. And cobalt naphthate. A redox initiator may be used independently or may use 2 or more types together.

  When a redox initiator is used, the redox initiator is present in a catalytically effective amount, and its addition amount is not particularly limited, but is preferred when the component (A) of the present invention is 100 parts by weight. Is about 0.01-5 parts by weight, more preferably about 0.025-2 parts by weight. Considering that the curable composition for filling between the flat panel display display module / transparent cover board is temporarily fixed with light such as UV, a photopolymerization initiator is mainly used among the above initiators. It is preferable.

<Curing catalyst (D)>
Although it does not specifically limit when (B) component is included in the curable composition of this invention, It is preferable to use a curing catalyst (D). The compound (B) having at least one hydrolyzable silyl group on average used in the present invention is present in the presence of various conventionally known condensation catalysts (sometimes referred to as curing catalysts or “curing agents”), or non- Crosslink and cure by forming siloxane bonds in the presence. As the properties of the cured product, a wide range from rubbery to resinous can be prepared depending on the molecular weight and main chain skeleton of the polymer.

  In the curable composition of the present invention, various conventionally known condensation catalysts used for polymers having a crosslinkable silyl group may be used.

  In the curable composition of the present invention, various conventionally known condensation catalysts used for the polymer having a crosslinkable silyl group may be used, but an organic metal, an acid catalyst, and an acid / base catalyst are preferable. A phosphoric acid catalyst and a phosphoric acid / amine catalyst are more preferable.

  Examples of the organometallic catalyst include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin diisosulfate. Octyl malate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diisooctylmalate, etc. Dialkyltin dicarboxylates such as dialkyltin alkoxides such as dibutyltin dimethoxide and dibutyltin diphenoxide, such as dibutyltin diacetylacetonate and dibutyltin die Intramolecular coordinating derivatives of dialkyltin such as rubacetoacetate, for example, reaction products of dialkyltin oxide such as dibutyltin oxide and dioctyltin oxide and ester compounds such as dioctylphthalate, diisodecylphthalate, and methyl maleate , A tin compound obtained by reacting a dialkyltin oxide, a carboxylic acid and an alcohol compound, for example, a reaction product of a dialkyltin oxide and a silicate compound such as dibutyltin bistriethoxysilicate, dioctyltin bistriethoxysilicate, and the dialkyltin compounds Tetravalent tin compounds such as oxy derivatives (stannoxane compounds) of the above; for example, divalent tin compounds such as tin octylate, tin naphthenate, tin stearate, tin ferrous acid, and the like Reaction products and mixtures of amines with amine compounds such as laurylamine; for example, monobutyltin compounds such as monobutyltin trisoctoate and monobutyltin triisopropoxide, and monoalkyltin compounds such as monooctyltin compounds; Titanates such as titanate, tetrapropyl titanate, tetra (2-ethylhexyl) titanate, isopropoxytitanium bis (ethylacetoacetate); aluminum trisacetylacetonate, aluminum trisethylacetoacetate, di-isopropoxyaluminum ethylacetoacetate, etc. Organoaluminum compounds: bismuth carboxylate, iron carboxylate, titanium carboxylate, lead carboxylate, vanadium carboxylate, zirconium carboxylate, calcium carbonate Carboxylic acids such as potassium, carboxylate, barium carboxylate, manganese carboxylate, cerium carboxylate, nickel carboxylate, cobalt carboxylate, zinc carboxylate, aluminum carboxylate (2-ethylhexanoic acid, neodecanoic acid, versatic acid, Oleic acid, naphthenic acid, etc.) Metal salts, or reaction products and mixtures of these with amine compounds such as laurylamine described later; zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, dibutoxyzirconium diacetylacetonate, zirconium Examples thereof include chelate compounds such as acetylacetonatobis (ethylacetoacetate) and titanium tetraacetylacetonate.

  Examples of the acid catalyst include sulfonic acid, carboxylic acid, phosphoric acid, nitric acid, and hydrofluoric acid catalysts. A sulfonic acid type, a phosphoric acid type, and a carboxylic acid type are preferable in terms of a balance between curing activity and storage stability. Specific examples include sulfuric acid, paratoluenesulfonic acid, dodecylbenzenesulfonic acid and the like as the sulfonic acid type.

  Specific examples of the carboxylic acid include acrylic acid, acetic acid, propionic acid, butyric acid, versatic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, and anhydrides thereof.

Examples of the phosphoric acid catalyst include phosphoric acid and organic phosphoric acid ester. More specifically, as the organic acidic phosphate ester compound of the acidic catalyst, (CH ₃ O) ₂ —P (═O) (— OH), (CH ₃ O) —P (═O) (— OH) _{2 , (C 2 H 5 O)} 2 -P (= O) (- OH), (C 2 H 5 O) -P (= O) (- OH) 2, (C 3 H 7 O) 2 -P ( _{= O) (- OH),} (C 3 H 7 O) -P (= O) (- OH) 2, (C 4 H 9 O) 2 -P (= O) (- OH), (C 4 H ₉ O) —P (═O) (— OH) ₂ , (C ₈ H ₁₇ O) ₂ —P (═O) (— OH), (C ₈ H ₁₇ O) —P (═O) (— OH) ) ₂ , (C ₁₀ H ₂₁ O) ₂ —P (═O) (— OH), (C ₁₀ H ₂₁ O) —P (═O) (— OH) ₂ , (C ₁₃ H ₂₇ O) ₂ — _{P (= O) (- OH} ), (C 13 H 27 O) - _{P (= O) (- OH} ) 2, (C 16 H 33 O) 2 -P (= O) (- OH), (C 16 H 33 O) -P (= O) (- OH) 2, ( _{HO-C 6 H 12 O)} 2 -P (= O) (- OH), (HO-C 6 H 12 O) -P (= O) (- OH) 2, (HO-C 8 H 16 O) _{-P (= O) (- OH} ), (HO-C 8 H 16 O) -P (= O) (- OH) 2, [(CH 2 OH) (CHOH) O] 2 -P (= O) (—OH), [(CH ₂ OH) (CHOH) O] —P (═O) (— OH) ₂ , [(CH ₂ OH) (CHOH) C ₂ H ₄ O] ₂ —P (═O) (—OH), [(CH ₂ OH) (CHOH) C ₂ H ₄ O] —P (═O) (— OH) _{2 and the} like are exemplified, but are not limited to the exemplified substances.

  Examples of the acid / base catalyst include a combination of the aforementioned acid catalyst and an amine compound described below. Among these, a combination of phosphoric acid and amine is preferable.

  Examples of amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, cyclohexylamine, etc. Aliphatic primary amines: dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine, dicetylamine, distearylamine, methylstearyl Aliphatic secondary amines such as amine, ethylstearylamine, butylstearylamine; triamylamine, trihexylamine Aliphatic tertiary amines such as trioctylamine; aliphatic unsaturated amines such as triallylamine and oleylamine; aromatic amines such as laurylaniline, stearylaniline and triphenylamine; and other amines, Monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,4 6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabi Amine compounds such as black (5,4,0) undecene-7 (DBU), polyamine compounds, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ- Aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, N- (β-aminoethyl) ) Aminopropyltriethoxysilane, N- (β-aminoethyl) aminopropylmethyldiethoxysilane, N- (β-aminoethyl) aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ -Aminopropyltrimethoxy Orchid, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, and the like. Moreover, amino groups such as silane coupling agents having amino groups such as amino-modified silyl polymer, silylated amino polymer, unsaturated aminosilane complex, phenylamino long chain alkylsilane, aminosilylated silicone, etc. Examples thereof include, but are not limited to the exemplified substances.

  When the acid / base catalyst is added, the acid catalyst and the base catalyst may be mixed and reacted in advance, or may be mixed later. If they are mixed and reacted in advance, the catalytic activity becomes higher and fast curability may be realized.

  The acid / base equivalent ratio (molar ratio) is 0.1-50 in terms of acid / base. 0.3-40 are preferable and 0.5-30 are preferable at the point of sclerosis | hardenability, pot life, and storage stability.

  The amount of these catalysts added is preferably about 0.01 to 50 parts by weight with respect to 100 parts by weight of the compound (B) having at least one hydrolyzable silyl group on average, and more preferably 0.1 to 20 parts by weight is more preferable.

<Combination agent>
In the curable composition of the present invention, various compounding agents may be added according to the intended physical properties.

[Monomer and / or oligomer (E)]
The curable composition of the present invention contains a compound (A) having an average of at least one polymerizable carbon-carbon double bond in one molecule, and the number average molecular weight of the component (A) is 5000 or more. In this case, a monomer and / or oligomer (E) having a (meth) acryloyl group and having a number average molecular weight of 5000 or less can be added as long as the effects of the present invention are not impaired.

  Specific examples of the monomer include those described in paragraphs [0123] to [0131] of JP-A-2006-265488.

  Examples of the oligomer include those described in paragraph [0132] of JP-A-2006-265488.

  The number average molecular weight of the monomer and / or oligomer having a (meth) acryloyl group is 5000 or less, but in the case of using a monomer in order to improve surface curability or reduce viscosity for improving workability. Further, it is more preferable that the molecular weight is 1000 or less because the compatibility is good.

  The amount of the monomer and / or oligomer (E) used is a total of 100 parts by weight (hereinafter referred to as “component (A)” and “component (B)”) from the viewpoint of improving surface curability, imparting toughness, and workability by reducing viscosity. 1 to 200 parts is preferable, and 5 to 100 parts is more preferable.

[Filler]
Although it does not specifically limit as a filler, The filler of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0158] is mentioned. Of these fillers, crystalline silica, fused silica, dolomite, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable. In particular, when it is desired to obtain a cured product having high strength with these fillers, mainly crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay and activity A filler selected from zinc oxide and the like can be added. Among them, the specific surface area (according to BET adsorption method) of ^{50 m} 2 / g or more, usually 50 to 400 m ² / g, is preferably 100 to 300 m ² / g approximately ultrafine powdery silica preferred. Further, silica whose surface has been previously hydrophobically treated with an organosilicon compound such as organosilane, organosilazane, diorganopolysiloxane, etc. is more preferred.

Moreover, when it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like can be added. In general, when calcium carbonate has a small specific surface area, the effect of improving the breaking strength and breaking elongation of the cured product may not be sufficient. The larger the specific surface area value, the greater the effect of improving the breaking strength and breaking elongation of the cured product.
Furthermore, it is more preferable that the calcium carbonate is subjected to a surface treatment using a surface treatment agent.

  When surface-treated calcium carbonate is used, the workability of the curable composition of the present invention is improved as compared with the case where calcium carbonate that is not surface-treated is used, and the storage stability effect of the curable composition is improved. It is thought that it will improve further.

  As the surface treatment agent, known ones can be used, and examples include surface treatment agents described in paragraph [0161] of JP-A-2005-232419. The treatment amount of the surface treatment agent is preferably in the range of 0.1 to 20% by weight and more preferably in the range of 1 to 5% by weight with respect to calcium carbonate. When the treatment amount is less than 0.1% by weight, the workability improving effect may not be sufficient, and when it exceeds 20% by weight, the storage stability of the curable composition may be lowered. Although there is no particular limitation, when calcium carbonate is used, colloidal calcium carbonate is preferably used when the effect of improving the thixotropy of the blend, the breaking strength of the cured product, the elongation at break and the like is particularly expected. On the other hand, those described in paragraph [0163] of JP-A-2005-232419 in which heavy calcium carbonate is sometimes added for the purpose of increasing the amount of the compound, reducing costs, or the like can be used.

  The said filler may be used independently according to the objective and necessity, and may use 2 or more types together. In the case of using a filler, it is preferable to use the filler in the range of 5 to 1000 parts by weight with respect to the total of 100 parts by weight of the component (A) and the component (B), and 20 to 500 parts by weight. More preferably, it is used in a range of 40 to 300 parts by weight. If the blending amount is less than 5 parts by weight, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient, and if it exceeds 1000 parts by weight, the work of the curable composition May decrease.

[Micro hollow particles]
For the purpose of reducing the weight and cost without causing a significant decrease in physical properties, fine hollow particles can be added in combination with these reinforcing fillers. Such fine hollow particles (hereinafter sometimes referred to as “balloons”) are not particularly limited, but have a diameter as described in “Latest Technology for Functional Fillers” (CMC). Examples thereof include hollow bodies (inorganic balloons and organic balloons) made of inorganic or organic materials of 1 mm or less, preferably 500 μm or less, more preferably 200 μm or less. In particular, it is preferable to use a micro hollow body having a true specific gravity of 1.0 g / cm ³ or less, and more preferably to use a micro hollow body having a specific gravity of 0.5 g / cm ³ or less.

  As the inorganic balloon and the organic balloon, balloons described in paragraphs [0168] to [0170] of JP-A-2005-232419 can be used. The balloons may be used alone or in combination of two or more. Furthermore, the surface of these balloons is made of fatty acid, fatty acid ester, rosin, rosin acid lignin, silane coupling agent, titanium coupling agent, aluminum coupling agent, polypropylene glycol, etc. to improve dispersibility and workability of the compound. Those processed in the above can also be used. These balloons are used for weight reduction and cost reduction without impairing flexibility and elongation / strength among physical properties when the compound is cured.

  The addition amount of the balloon is not particularly limited, but is preferably in the range of 0.1 to 50 parts by weight, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the total of component (A) and component (B). Can be used in If the amount is less than 0.1 parts by weight, the effect of reducing the weight is small. If the amount is more than 50 parts by weight, a decrease in tensile strength may be observed among the mechanical properties when the compound is cured. Moreover, when the specific gravity of a balloon is 0.1 or more, the addition amount is preferably 3 to 50 parts by weight, more preferably 5 to 30 parts by weight.

[Antioxidant]
Various antioxidants may be used in the curable composition of the present invention as necessary. These antioxidants include p-phenylenediamine-based antioxidants, amine-based antioxidants, hindered phenol-based antioxidants, secondary antioxidants such as phosphorus-based antioxidants, sulfur-based antioxidants, etc. Is mentioned.

[Plasticizer]
A plasticizer can be mix | blended with the curable composition of this invention as needed.
Although it does not specifically limit as a plasticizer, For example, the plasticizer of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0173] is mentioned by the objectives, such as adjustment of a physical property and adjustment of a property. Among these, polyester plasticizers and vinyl polymers are preferable because the effect of reducing the viscosity is remarkable and the volatilization rate during the heat resistance test is low. Further, by adding a polymer plasticizer which is a polymer having a number average molecular weight of 500 to 15000, the viscosity of the curable composition and the tensile strength and elongation of the cured product obtained by curing the curable composition are added. The mechanical properties such as the above can be adjusted, and the initial physical properties can be maintained over a long period of time as compared with the case where a low molecular plasticizer which is a plasticizer not containing a polymer component in the molecule is used. Although not limited, the polymer plasticizer may or may not have a functional group.

  Although the number average molecular weight of the said polymeric plasticizer was described as 500-15000, Preferably it is 800-10000, More preferably, it is 1000-8000. If the molecular weight is too low, the plasticizer may flow out over time when exposed to heat or in contact with a liquid, and the initial physical properties may not be maintained over a long period of time. Moreover, when molecular weight is too high, a viscosity will become high and there exists a tendency for workability | operativity to fall.

  Of these polymer plasticizers, those compatible with the vinyl polymer are preferred. Of these, vinyl polymers are preferred from the viewpoints of compatibility, weather resistance, and heat aging resistance. Among the vinyl polymers, (meth) acrylic polymers are preferable, and acrylic polymers are more preferable. Examples of the method for synthesizing the acrylic polymer include those obtained by conventional solution polymerization and solvent-free acrylic polymers. The latter acrylic plasticizer does not use a solvent or a chain transfer agent, and is a high-temperature continuous polymerization method (USP 4414370, JP 59-6207, JP-B-5-58005, JP 1-331522, USP 5010166). It is more preferable for the purpose of the present invention. Examples thereof include, but are not limited to, Toagosei UP series and the like (see the Industrial Materials October 1999 issue). Of course, the living radical polymerization method can also be mentioned as another synthesis method. According to this method, the molecular weight distribution of the polymer is narrow and the viscosity can be lowered, and the atom transfer radical polymerization method is more preferable, but it is not limited thereto.

  The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and is preferably less than 1.8. 1.7 or less is more preferable, 1.6 or less is still more preferable, 1.5 or less is more preferable, 1.4 or less is especially preferable, and 1.3 or less is the most preferable.

The plasticizer containing the above-mentioned polymer plasticizer may be used alone or in combination of two or more, but is not necessarily required. Further, if necessary, a high molecular plasticizer may be used, and a low molecular plasticizer may be further used in a range that does not adversely affect the physical properties.
These plasticizers can also be blended at the time of polymer production.

  Although the usage-amount in the case of using a plasticizer is not limited, Preferably it is 1-100 weight part with respect to 100 weight part of (A) component and (B) component total, More preferably, it is 5-50 weight part. If the amount is less than 1 part by weight, the effect as a plasticizer tends to be hardly exhibited, and if it exceeds 100 parts by weight, the mechanical strength of the cured product tends to be insufficient.

[Reactive diluent]
In addition to the plasticizer, a reactive diluent described below may be used in the present invention. If a low-boiling compound that can be volatilized during curing is used as a reactive diluent, it will change shape before and after curing, or it may adversely affect the environment due to volatiles. An organic compound having a boiling point of 100 ° C. or higher is particularly preferable.

  Specific examples of the reactive diluent include 1-octene, 4-vinylcyclohexene, allyl acetate, 1,1-diacetoxy-2-propene, methyl 1-undecenoate, 8-acetoxy-1,6-octadiene and the like. However, it is not limited to these.

  The amount of the reactive diluent added is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 70 parts by weight, and still more preferably 1 with respect to 100 parts by weight of the total of the components (A) and (B). ~ 50 parts by weight.

[Light stabilizer]
You may add a light stabilizer to the curable composition of this invention as needed. Various types of light stabilizers are known, and are described in, for example, “Antioxidant Handbook” issued by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242) issued by CM Chemical Co., Ltd. Although various things are mentioned, it is not necessarily limited to these.

  Although not particularly limited, among the light stabilizers, ultraviolet absorbers are preferable. Specifically, TINUVIN P, TINUVIN 234, TINUVIN 320, TINUVIN 326, TINUVIN 327, TINUVIN 329, TINUVIN 213 (all of which are Nippon Ciba Geigy Corporation) Benzotriazole compounds such as Tinuvin 1577, benzophenone compounds such as CHIMASSORB 81, and benzoate compounds such as Tinuvin 120 (manufactured by Ciba Geigy Japan).

  Further, hindered amine compounds are also preferable, and specific examples of such compounds include those described in JP-A-2006-274084, but are not limited thereto. Furthermore, since the combination of the ultraviolet absorber and the hindered amine compound may exhibit more effect, it is not particularly limited, but may be used in combination, and it is preferable to use in combination.

  The light stabilizer may be used in combination with the above-described antioxidant, and it is particularly preferable because the effect is further exhibited and the weather resistance may be improved. Tinuvin C353, Tinuvin B75 (all of which are manufactured by Ciba Geigy Japan, Inc.) in which a light stabilizer and an antioxidant are mixed in advance may be used.

  It is preferable that the usage-amount of a light stabilizer is the range of 0.1-10 weight part with respect to 100 weight part of (A) component and (B) component total. If the amount is less than 0.1 parts by weight, the effect of improving the weather resistance is small.

[Adhesive agent]
An adhesiveness-imparting agent can be added to the curable composition of the present invention for the purpose of further improving the substrate adhesion. Examples of the adhesiveness-imparting agent include a crosslinkable silyl group-containing compound and a vinyl group having a polar group. A monomer is preferable, and further, a silane coupling agent and an acidic group-containing vinyl monomer are preferable. Specific examples thereof include the adhesion-imparting agent described in paragraph [0184] of JP-A-2005-232419.

  As silane coupling agents, other than carbon atoms and hydrogen atoms, such as epoxy groups, isocyanate groups, isocyanurate groups, carbamate groups, amino groups, mercapto groups, carboxyl groups, halogen groups, (meth) acryl groups, etc. in the molecule. A silane coupling agent having both an organic group having an atom and a crosslinkable silyl group can be used.

  Specific examples thereof include a silane coupling agent having both a crosslinkable silyl group and an organic group having atoms other than carbon atoms and hydrogen atoms described in paragraph [0185] of JP-A-2005-232419. Among these, alkoxysilanes having an epoxy group or a (meth) acryl group in the molecule are more preferable from the viewpoint of curability and adhesiveness.

  As a vinyl monomer having a polar group, as a carboxyl group-containing monomer, (meth) acrylic acid, acryloxypropionic acid, citraconic acid, fumaric acid, itaconic acid, crotonic acid, maleic acid or esters thereof, And maleic anhydride and derivatives thereof. Examples of the ester of the galboxyl group-containing monomer include 2- (meth) acryloyloxyethyl succinic acid and 2- (meth) acryloyloxyethyl hexahydrophthalic acid. Examples of the sulfonic acid group-containing monomer include vinyl sulfonic acid, (meth) acryl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, vinyl benzene sulfonic acid, 2-acrylamido-2-methylpropane sulfone, and salts thereof. Can be mentioned. Furthermore, as phosphoric acid group-containing monomers, 2-((meth) acryloyl cyethyl phosphate), 2- (meth) acryloyloxypropyl phosphate, 2- (meth) acryloyloxy-3-chloropropyl phosphate, 2- Examples include (meth) acryloyloxyethyl phenyl phosphate. Of these, phosphate group-containing monomers are preferred. The monomer may have two or more polymerizable groups.

  Specific examples of the adhesion-imparting agent other than the silane coupling agent and the polar group-containing vinyl monomer are not particularly limited. For example, epoxy resins, phenol resins, modified phenol resins, cyclopentadiene-phenol resins, xylene resins , Coumarone resin, petroleum resin, terpene resin, terpene phenol resin, rosin ester resin sulfur, alkyl titanates, aromatic polyisocyanate and the like.

  The adhesiveness-imparting agent is preferably blended in an amount of 0.01 to 20 parts by weight with respect to 100 parts by weight as a total of the components (A) and (B). If the amount is less than 0.01 part by weight, the effect of improving the adhesiveness is small, and if it exceeds 20 parts by weight, the physical properties of the cured product tend to be lowered. Preferably it is 0.1-10 weight part, More preferably, it is 0.5-5 weight part.

  The adhesiveness-imparting agent may be used alone or in combination of two or more.

[solvent]
A solvent can be mix | blended with the curable composition of this invention as needed. Solvents that can be blended include, for example, aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone A solvent etc. are mentioned. These solvents may be used during production of the polymer.

[Other additives]
Various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or its cured product. Examples of such additives include, for example, flame retardants, anti-aging agents, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, etc. Can be given. These various additives may be used alone or in combination of two or more. Specific examples of such additives include, for example, each specification of JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, and the like. It is described in.

  The curable composition of the present invention can be prepared as a one-pack type in which all blending components are blended and sealed in advance, and the A liquid from which only the initiator is removed and the initiator is mixed with a filler, a plasticizer, a solvent, and the like. It can also be prepared as a two-component type in which the prepared B solution is mixed immediately before molding.

<< Usage >>
Examples of the display device of the present invention include a liquid crystal touch panel, an organic EL touch panel, a liquid crystal module, a PDP, a digital and an analog speedometer.

  In a liquid crystal touch panel, an organic EL touch panel, a liquid crystal module, and a PDP, the liquid curable composition of the present invention can be used between a cover glass and a touch sensor, between a touch sensor and an LCDM (liquid crystal module), or the like.

  Digital and analog speedometers can be used between the speedometer and the protective cover.

  The display device is mounted on electric / electronic devices / motorcycles and automobiles.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.
In the following examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column filled with polystyrene cross-linked gel (shodex GPC K-804 and K-802.5; Showa Denko KK) and chloroform as a GPC solvent were used.
¹ H-NMR was measured at 23 ° C. using Bruker ASX-400 (400 MHz) and deuterated chloroform as a solvent.
In the following examples, “average terminal crosslinkable silyl group or (meth) acryloyl group number” is “number of crosslinkable silyl groups introduced per polymer molecule, (meth) acryloyl group number”, and ¹ H-NMR analysis. And the number average molecular weight determined by GPC.
In the examples and comparative examples below, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

<Manufacture of oxyalkylene polymer having (meth) acryloyloxy group at terminal>
(Production Example 1)
Polyoxypropylene having a GPC measurement (polystyrene conversion) number average molecular weight of 10800 and Mw / Mn of 1.2 by polymerizing propylene oxide using Actocol P-23 as an initiator and a zinc hexacyanocobaltate glyme complex Glycol was produced and 1.1 equivalents of 2-acryloyloxyethyl isocyanate were reacted with the hydroxyl group to obtain a polymer [P1] having a radical reactive double bond at the terminal.

<Production of (meth) acrylic polymer having (meth) acryloyloxy group at terminal>
(Production Examples 2, 3, 4)
Table 1 shows the amount of each raw material used.
(1) Polymerization process n-butyl acrylate was deoxygenated. The inside of the stainless steel reaction vessel equipped with a stirrer was deoxygenated, and cuprous bromide and a part of n-butyl acrylate (described as initial charge monomer in Table 1) were charged and stirred with heating. A stage in which acetonitrile (described as “Acetonitrile for polymerization” in Table 1) and diethyl-2,5-dibromoadipate (DBAE) or ethyl 2-bromobutyrate as an initiator were added and mixed, and the temperature of the mixture was adjusted to about 80 ° C. Then, pentamethyldiethylenetriamine (hereinafter abbreviated as triamine) was added to initiate the polymerization reaction. The remaining acrylic ester (described as an additional monomer in Table 1) was added sequentially to proceed the polymerization reaction. During the polymerization, triamine was appropriately added to adjust the polymerization rate. The total amount of triamine used during the polymerization is shown in Table 1 as a triamine for polymerization. As the polymerization proceeds, the internal temperature rises due to the heat of polymerization, so the polymerization was allowed to proceed while adjusting the internal temperature to about 80 ° C to about 90 ° C.
(2) Oxygen treatment step When the monomer conversion rate (polymerization reaction rate) was about 95% or more, an oxygen-nitrogen mixed gas was introduced into the gas phase part of the reaction vessel. While maintaining the internal temperature at about 80 ° C. to about 90 ° C., the reaction solution was heated and stirred for several hours to bring the polymerization catalyst in the reaction solution into contact with oxygen. Acetonitrile and unreacted monomer were removed by devolatilization under reduced pressure to obtain a concentrate containing a polymer. The concentrate was markedly colored.
(3) First crudely purified butyl acetate was used as a diluent solvent for the polymer. The concentrate of (2) was diluted with about 100 to 150 kg of butyl acetate with respect to 100 kg of the polymer, and a filter aid (Radiolite R900, Showa Chemical Industry Co., Ltd.) was added. After introducing an oxygen-nitrogen mixed gas into the gas phase part of the reaction vessel, the mixture was heated and stirred at about 80 ° C. for several hours. Insoluble catalyst components were removed by filtration. The filtrate was colored and slightly turbid due to the polymerization catalyst residue.
(4) The second crude purified filtrate was charged into a stainless steel reaction vessel equipped with a stirrer, and adsorbents (Kyoward 700SEN, Kyoward 500SH) were added. After introducing an oxygen-nitrogen mixed gas into the gas phase and heating and stirring at about 100 ° C. for several hours, insoluble components such as an adsorbent were removed by filtration. The filtrate was almost clear and clear. The filtrate was concentrated to obtain an almost colorless and transparent polymer.
(5) (Meth) acryloyl group introduction step 100 kg of polymer is dissolved in about 100 kg of N, N-dimethylacetamide (DMAC), and potassium acrylate (about 2 molar equivalents relative to the terminal Br group), thermal stabilizer (H -TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl) and an adsorbent (Kyoward 700SEN) were added, and the mixture was heated and stirred at about 70 ° C for several hours. DMAC was distilled off under reduced pressure, the polymer concentrate was diluted with about 100 kg of toluene with respect to 100 kg of the polymer, a filter aid was added, the solid content was filtered off, the filtrate was concentrated, and an acryloyl group was added to the end. Polymers [P2], [P3] and [P4] having Table 1 shows the number of acryloyl groups introduced per molecule of the obtained polymer, the number average molecular weight, and the molecular weight distribution.

<Production of hydrolyzable silyl group-containing oxyalkylene polymer>
(Production Example 5)
GPC measurement (polystyrene conversion) number average molecular weight 10800 by polymerizing propylene oxide using Actocol P-23 (manufactured by Mitsui Takeda Co., Ltd., polyoxypropylene glycol) as an initiator and a zinc hexacyanocobaltate glyme complex. Polyoxypropylene glycol having Mw / Mn of 1.2 was produced, and then the terminal hydroxyl group was metaloxylated. Further, allyl chloride is reacted to introduce unsaturated groups at all terminals, and then methyldimethoxysilane is reacted to 0.75 equivalents with respect to the unsaturated groups to obtain a polymer [P5] having methyldimethoxysilyl groups at the terminals. It was.

<Production of hydrolyzable silyl group-containing (meth) acrylic polymer>
(Production Examples 6 and 7)
Table 2 shows the amount of each raw material used.
(1) Polymerization process n-butyl acrylate was deoxygenated. The inside of the stainless steel reaction vessel with a stirrer was deoxygenated, and cuprous bromide and a part of n-butyl acrylate (described as the initial charge monomer in Table 2) were charged and stirred with heating.
Acetonitrile (described as “Acetonitrile for polymerization” in Table 2) and diethyl-2,5-dibromoadipate as an initiator were added and mixed. At the stage where the temperature of the mixture was adjusted to about 80 ° C., pentamethyldiethylenetriamine (hereinafter triamine and (Omitted) was added to initiate the polymerization reaction. The remaining n-butyl acrylate (described as an additional monomer in Table 2) was sequentially added to proceed the polymerization reaction. During the polymerization, triamine was appropriately added to adjust the polymerization rate. The total amount of triamine used during polymerization is shown in Table 2 as polymerization triamine. As the polymerization proceeds, the internal temperature rises due to the heat of polymerization, so the polymerization was allowed to proceed while adjusting the internal temperature to about 80 ° C to about 90 ° C.
When the monomer conversion rate (polymerization reaction rate) was about 95% or more, volatile components were removed by devolatilization under reduced pressure to obtain a polymer concentrate.
(2) Diene reaction step 1,7-octadiene (hereinafter abbreviated as diene or octadiene) and acetonitrile (referred to as diene reaction acetonitrile in Table 2) were added to the concentrate, and a triamine (in Table 2, triamine for diene reaction) Added). While adjusting the internal temperature to about 80 ° C. to about 90 ° C., the mixture was heated and stirred for several hours to react the octadiene with the polymer terminal. Acetonitrile and unreacted octadiene were removed by devolatilization under reduced pressure to obtain a concentrate containing a polymer having an alkenyl group at the terminal.
(3) Rough purification step The above concentrate is diluted with toluene, filter aid, adsorbent (KYOWARD 700SEN: manufactured by Kyowa Chemical Industry Co., Ltd.), hydrotalcite (KYOWARD 500SH: Kyowa Chemical Industry Co., Ltd.)
Product) was added and heated and stirred at about 80 to 100 ° C., and then the solid components were filtered off. The filtrate was concentrated to obtain a crude polymer product.
(4) High-temperature heat treatment / adsorption purification process Crude polymer product, heat stabilizer (Sumilyzer GS: manufactured by Sumitomo Chemical Co., Ltd.), adsorbent (Kyoward 700SEN, Kyoward 500SH) are added, and devolatilization under reduced pressure. The temperature was raised while heating and stirring, and heating and stirring and vacuum devolatilization were performed for about several hours at a high temperature of about 170 ° C to about 200 ° C. Adsorbents (Kyoward 700SEN, Kyoward 500SH) were added, about 10 parts by weight of toluene was added to the polymer, and the mixture was further heated and stirred at a high temperature of about 170 ° C. to about 200 ° C. for several hours.
The treatment liquid was further diluted with toluene, and the adsorbent was filtered off. The filtrate was concentrated to obtain a polymer having alkenyl groups at both ends.
(5) Silylation step Polymer obtained by the above method, methyldimethoxysilane (DMS), methyl orthoformate (MOF), platinum catalyst [bis (1,3-divinyl-1,1,3,3-tetramethyl A predetermined amount of (disiloxane) platinum complex catalyst in isopropanol solution: hereinafter referred to as platinum catalyst] was mixed and heated to about 100 ° C. with stirring. After heating and stirring for about 1 hour, volatile components such as unreacted DMS were distilled off under reduced pressure to obtain polymers [P6] and [P7] having methoxysilyl groups at both ends. The number of silyl groups introduced per molecule of the obtained polymer, the molecular weight, and the molecular weight distribution are shown together in Table 2.

Example 1
(A) 50 parts of the polymer [P1] obtained in Production Example 1 as the component, 50 parts of the polymer [P5] obtained in Production Example 5 as the (B) component, IBXA (isobornyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd.) ) 10 parts, (C) component, DAROCUR1173 (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one, manufactured by Ciba Specialty Chemicals) 0.1 part, IRGACURE819 (bis ( 2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by Ciba Specialty Chemicals) 0.05 part, SILQUESTA 171 (vinyltrimethoxysilane, manufactured by Momentive) 2 parts, and further, AP- 8 (2-ethylhexyl acid phosphate, manufactured by Eighth Chemical Industry Co., Ltd.) 0.33 parts, DBU (1 8-diazabicyclo [5,4,0] -7-undecene) 0.02 parts to prepare a combined curable composition 1 adhered was thoroughly mixed by stirring. The above liquid curable composition 1 was applied to a PET substrate having a width of 100 mm and a length of 100 mm so as to have a thickness of 500 μm. H. And left for 1 day to obtain a gel sheet. The gel sheet is bonded so that there is no foam so that it is sandwiched between a 20-inch touch panel with FPC (flexible heat-resistant electrode) and a cover glass with black printing of the same size, and a conveyor-type UV irradiation device (light A touch panel PC monitor was manufactured by completely curing with a hammer 6 (Fusion UV system, integrated light quantity 6000 mJ / cm ² ). The following adhesion durability and visibility were evaluated using the obtained display device. The results are shown in Table 3.

(Adhesion durability evaluation)
The obtained display device was placed in an atmosphere of 60 ° C. and 95% humidity for 250 hours, and then the adhesion durability was evaluated by visual observation. The thing without peeling was set as (circle), and the thing with peeling was set as x.

(Visibility evaluation)
The obtained display device was visually evaluated. When the display screen was visually observed under direct sunlight, the case where the display screen was clearly identifiable was rated as ◯, and when the display was not clearly identifiable under the same conditions, or the image was white and blurred, it was marked as x.

(Example 2)
60 parts of the polymer [P3] obtained in Production Example 3 as the component (A), 40 parts of the polymer [P6] obtained in Production Example 6 as the component (B), 30 parts of IBXA, V-192 (phenoxyethyl acrylate) , Osaka Organic Chemical Industry) 10 parts, 4-HBA (4-hydroxybutyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd.) 10 parts, (C) Component, DAROCUR1173 0.4 part, IRGACURE819 0.2 part, SILQUESTA 171 2 parts, 2 parts of KBM-5103 (trimethoxysilylpropyloxyacrylate, manufactured by Shin-Etsu Chemical Co., Ltd.), 1 part of AP-8 and 0.06 part of DBU as the component (D) are sufficiently stirred and mixed to obtain a curable composition 2 for bonding. Prepared. The curable composition 2 is uniformly applied to a PMMA film so as to have a film thickness of 200 μm, and is cured in a gel form by a conveyor type UV irradiation device (light hammer 6; Fusion UV system, integrated light quantity 6000 mJ / cm ² ). Furthermore, a release film was attached to obtain a gel sheet. The gel sheets were bonded together without bubbles so as to be sandwiched between 8-inch LCDM and a cover board with black printing. Curing was performed at 23 ° C. × 55% for 4 days to obtain a car navigation type image display device. The obtained image display apparatus was evaluated for adhesion durability and visibility as in Example 1. The results are shown in Table 3.

(Example 3)
(A) 20 parts of [P2], [P4] 40 parts, [P7] 40 parts, IBXA 10 parts, FA-513M (dicyclopentanyl methacrylate, manufactured by Hitachi Chemical Co., Ltd.) 14 parts, DAROCUR 1173 0.6 parts , IRAGCURE 819 0.3 part, SILQUESTA 171 6 part, KBM-5103 1 part, AP-8 0.33 part, DBU 0.02 part, AEROSIL # 200 (manufactured by Nippon Aerosil Co., Ltd.) 6 parts A curable composition 3 was obtained. The curable composition 3 was applied to a polycarbonate sheet with a thickness of 2 mm, degassed under a reduced pressure of 3.5 × 10 ⁻¹ MPa, and then 23 ° C. × 55% R.D. H. And left for 1 day to obtain a gel sheet. The gel sheet is bonded to the speed meter display part, and then a speed display pointer is attached, and then a protective cover is bonded to the conveyor type UV irradiation device (light hammer 6; Fusion UV system, integrated light quantity 6000 mJ / cm ^2. ) Was completely cured to produce a speed meter. Visibility and the following weather resistance and workability were evaluated using the obtained display device. The results are shown in Table 3.

(Weather resistance evaluation)
The obtained display device was cured for 1000 hours with SWM (Sunshine Weather Meter S300, Suga Test Instruments Co., Ltd., condition: 180 W / m ² ), and then the adhesion durability was visually evaluated. When there was no abnormality when the sample was visually confirmed, the sample was evaluated as “◯”, and the sample causing defects such as whitening and discoloration was evaluated as “X”.

(Processability evaluation)
A hole for passing a needle for speed display was formed by boring and cutting in the gel part of the member where the gel sheet and the speed meter display part were bonded together, and then the pointer was attached. If there was no crack etc. in the gel of the obtained speed meter, it was set as (circle) and if there was a crack, it was set as x.

(Comparative Example 1)
A PC monitor was produced in the same manner as in Example 1 except that the curable composition 1 of Example 1 was directly applied and UV cured. In the same manner as in Example 1, the adhesion durability and visibility were evaluated. The results are shown in Table 3.

(Comparative Example 2)
A speed meter was produced in the same manner as in Example 3, except that the curable composition 3 of Example 3 was directly applied to a speed display meter, UV and moisture cured, and then a display pointer was attached. As in Example 3, the visibility, weather resistance, and workability were evaluated.
The results are shown in Table 3.

  From a comparison between Examples 1 to 3 and Comparative Examples 1 and 2, it was found that the Examples exhibited an effect excellent in adhesion durability and workability of the FPC portion.

  According to the present invention, in order to improve the visibility and impact resistance of a liquid crystal touch panel, an organic EL touch panel, a liquid crystal module, and a PDP, when the air gap portion is filled with resin, it is applied in a liquid state. Rather, the liquid resin is pre-cured with active energy rays or a gel-like substance cured at room temperature, and then cured completely at room temperature or with active energy rays. A liquid crystal touch panel, an organic EL touch panel, a liquid crystal module, a PDP, a digital and analog speedometer, and an electric / electronic device / motorcycle equipped with them, and a method for manufacturing an automobile can be provided.

Claims (27)

A method for manufacturing a display device in which a resin layer is formed between a first member and a second member, and the method for manufacturing a display device through the following three steps.
(1) The process which makes a liquid curable composition a gel-like material by active energy ray hardening and / or normal temperature hardening.
(2) The process of bonding so that a gel-like thing may be inserted | pinched between a 1st member and a 2nd member.
(3) A step of completely curing the gel-like material by normal temperature curing and / or active energy ray curing. In the step (2), after the gel material and the first member are bonded together, the parts are attached to the surface of the gel material or the first substrate, and then the gel material and the second member are attached. The method for manufacturing a display device according to claim 1, wherein bonding is performed. The method for manufacturing a display device according to claim 1, wherein the room temperature curing is moisture curing. The method of manufacturing a display device according to claim 1, wherein the active energy ray is selected from EB (electron beam) and UV. 4. The method for manufacturing a display device according to claim 1, wherein the active energy ray is UV. The liquid curable composition (A) having an average of at least one polymerizable carbon-carbon double bond in one molecule and a compound having an average of at least one hydrolyzable silyl group in one molecule ( B) is included, The manufacturing method of the display apparatus in any one of Claims 1-5 characterized by the above-mentioned. A liquid curable composition contains a polymerization initiator (C), The display apparatus manufacturing method in any one of Claims 1-6 characterized by the above-mentioned. The method for manufacturing a display device according to claim 7, wherein the polymerization initiator (C) is selected from at least one of a photopolymerization initiator and a redox initiator. The method for producing a display device according to claim 7, wherein the polymerization initiator (C) is a photopolymerization initiator. The method for producing a display device according to any one of claims 1 to 9, wherein the liquid curable composition contains a curing catalyst (D). The method for manufacturing a display device according to claim 10, wherein the curing catalyst (D) is selected from at least one of an organic metal, an acid catalyst, and an acid / base catalyst. 11. The method for manufacturing a display device according to claim 10, wherein the curing catalyst (D) is selected from at least one of an organic tin catalyst, a phosphoric acid catalyst, and a phosphoric acid / amine catalyst. The display according to any one of claims 6 to 12, wherein the component (A) and / or the component (B) is at least one selected from polysiloxanes, polyethers, and vinyl polymers. Device manufacturing method. (A) component and / or (B) component is polyoxyethylene, polyoxypropylene, polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, (meth) acrylic monomer, acrylonitrile monomer, aromatic vinyl The monomer according to any one of claims 6 to 12, which is at least one selected from a polymer produced by mainly polymerizing a monomer selected from the group consisting of a monomer, a fluorine-containing vinyl monomer and a silicon-containing vinyl monomer. A method for manufacturing the display device according to claim 1. The component (A) and / or the component (B) is at least one selected from polyoxyethylene, polyoxypropylene, polyisobutylene, and a (meth) acrylic polymer. 12. A method for manufacturing a display device according to any one of claims 12 to 13. The method for manufacturing a display device according to claim 6, wherein the component (A) and / or the component (B) is a (meth) acrylic polymer. The method for manufacturing a display device according to claim 6, wherein the component (A) and / or the component (B) is an acrylic polymer. The method for manufacturing a display device according to any one of claims 6 to 12, wherein the component (A) and / or the component (B) is an acrylate polymer. The polymerizable carbon-carbon double bond of the component (A) has the general formula (1)
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
The method for manufacturing a display device according to claim 6, wherein the display device is a group represented by the formula: The display device according to any one of claims 6 to 19, wherein the hydrolyzable silyl group of the component (B) is represented by the general formula (101).
_{^{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (101)
(In the formula, R ¹ and R ² are the same or different and each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO. (In the formula, R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. The plurality of R ′ may be the same or different. When two or more R ¹ or R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and two or more Y are present. , They may be the same or different, a represents 0, 1, 2, or 3. b represents 0, 1, or 2. m represents an integer of 0 to 19. A + mb ≧ 1). The number average molecular weight of (A) component is 5000 or more, The manufacturing method of the display apparatus in any one of Claims 13-20 characterized by the above-mentioned. The method for producing a display device according to claim 21, further comprising a monomer and / or an oligomer (E) having a (meth) acryloyl group and having a number average molecular weight of 5000 or less. The method for manufacturing a display device according to any one of claims 13 to 22, wherein the molecular weight distribution of the components (A) and (B) is less than 1.8. 24. The method for manufacturing a display device according to claim 13, wherein the main chains of the components (A) and (B) are manufactured by a living polymerization method. The display according to any one of claims 13 to 24, wherein the polymerizable carbon-carbon double bond of component (A) and / or the hydrolyzable silyl group of component (B) is at the end of the molecular chain. Device manufacturing method. The display device manufacturing method according to any one of claims 1 to 25, wherein the display device is a liquid crystal touch panel, an organic EL touch panel, a liquid crystal module, a PDP, a digital and an analog speedometer. 27. An electric / electronic device, a motorcycle, or an automobile on which the display device obtained by the manufacturing method according to claim 1 is mounted.