WO2018012396A1 - Curable composition and product - Google Patents

Abstract

Provided are: a curable composition which contains an organic polymer that enables the progression of an adequate curing reaction by considerably suppressing polymerization inhibition by oxygen even if used in air, while being capable of ensuring a degree of freedom of design of the composition; and a product. This curable composition contains (A) an organic polymer that has a group represented by general formula (1), and at least one initiator selected from the group consisting of (B1) a photoinitiator and (B2) a thermal initiator. (In general formula (1), R¹ represents -H or -CH₃; and X represents a linking group, which is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a polar linking group (a (thio)ether linking group, an -O-CO- linking group, an -O-CO-NH- linking group, an -NR²- linking group (wherein R² represents a hydrogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a heterocyclic structure-containing group or a group having a plurality of rings)), or a direct bond.)

Description

Curable composition and product

The present invention relates to a curable composition and a product. In particular, the present invention relates to a curable composition containing an organic polymer having a group that suppresses polymerization inhibition by oxygen, and a product.

Conventionally, a photocurable pressure-sensitive adhesive composition containing a (meth) acrylate oligomer having a polyisoprene as a skeleton and a hydrogenated terpene phenol tackifier is known (for example, see Patent Document 1). In Patent Document 1, the photocurable pressure-sensitive adhesive composition according to Patent Document 1 is applied onto a PET film, covered with a PET film that has been subjected to a double-sided release treatment from above the coated surface, and irradiated with UV light. A cured product having adhesiveness is obtained. According to the photocurable pressure-sensitive adhesive composition according to Patent Document 1, it is possible to provide a photocurable pressure-sensitive adhesive composition that is excellent in workability at the time of dissolution preparation and coating, and gives a cured product having excellent adhesive strength and transparency. .

Further, in photo radical curing, inhibition of photo curing by oxygen is a problem, and photo curing of a thin film is particularly difficult. That is, radicals are generated by photolysis of the initiator, and these radicals attack the double bonds in the monomer and oligomer. In the absence of oxygen, this reaction is repeated and the polymerization is finally terminated by the bonding of radicals. However, when oxygen is present, the generated radicals capture oxygen and peroxy radicals are generated. Since peroxy radicals are stable and do not cause radical polymerization with a double bond, the reaction ends at the stage of peroxy radical generation. In particular, the thinner the coating film of the curable composition, the greater the influence of oxygen curing inhibition.

Therefore, for example, the following various countermeasures have been proposed (for example, see Non-Patent Document 1). That is, (a) a method of physically shielding oxygen, (b) a method of selecting an initiator system, (c) a method of selecting a monomer, and (d) a method of using thiol / ene photocuring. The method (a) is a method of photocuring in a nitrogen atmosphere, a carbon dioxide atmosphere or the like. The method (b) is a method of increasing the initiator concentration, and this method utilizes the fact that by increasing the concentration of the initiator and increasing the concentration of the starting radical, the number of radicals that do not react with oxygen also increases. ing. In particular, in preparation for the generation of peroxy radicals, there have been proposed a method of suppressing polymerization inhibition by using together with an amine that easily removes hydrogen, and a method of using a compound containing an amino group in an initiator.

As the method of (c), a method using a polyfunctional monomer (a polyfunctional monomer suppresses inhibition of polymerization of oxygen), a method using a monomer having a hydroxyl group, a method using an N-vinylamide monomer (N-vinylamide monomer) Suppresses the inhibition of polymerization of oxygen), a method utilizing a spacer such as polypropylene glycol diacrylate, and a method utilizing an additive (phosphorus-based secondary oxidation degradation inhibitor). The method using a monomer having a hydroxyl group is that a hydrogen atom bonded to the α-carbon of the hydroxyl group is easily extracted, so that even if a peroxy radical is generated, a hydrogen atom is further provided to easily generate a new carbon radical. Alternatively, the inhibition of curing is suppressed by utilizing the fact that a monomer having a hydroxyl group or a carboxyl group in the monomer is hydrogen-bonded between molecules.

(D) is a method in which thiol coexists. In this method, a thiol having a small SH bond energy is reacted with a peroxy radical to generate a thiyl radical, thereby inhibiting oxygen polymerization inhibition.

However, in the photocurable pressure-sensitive adhesive composition described in Patent Document 1, it is necessary to block the photocurable pressure-sensitive adhesive composition from outside air with a PET film or the like when light is irradiated. Not only is the object to which the agent composition can be applied limited, it takes time and effort to obtain a cured product having tackiness.

In addition, in “(a) Method of physically shielding oxygen” described in Non-Patent Document 1, the curable composition cannot be handled in the air, and “(b) an initiator system is selected. In the “method”, not only the amount of initiator added and the amount of amine added is limited, but there is a problem that a new active site is generated in the low molecular weight compound and the polymerization does not proceed appropriately. In addition, in the “(c) method for selecting a monomer”, when a polyfunctional monomer is used, a cured product of the curable composition is hard and brittle because a large number of crosslinking points are included in the polyfunctional monomer. There's a problem. And when using the monomer which has a hydroxyl group, although the polymerization inhibition by oxygen is suppressed to some extent, the effect is inadequate. Further, when N-vinylamide monomer is used, since the polarity of this compound is high, there is a problem that compatibility with other compounding substances is poor, and a cured product obtained by curing is also hard. There is a problem that the effect of suppressing polymerization inhibition is small. In addition, the method using a phosphorus-based secondary oxidation degradation inhibitor has a problem that the effect lasts only for about 24 hours after the addition of this inhibitor. The “(d) method using thiol / ene photocuring” has a problem that storage stability is poor due to the presence of a mercapto group. Furthermore, since a polyfunctional vinyl compound and a polyfunctional thiol are combined and photocured, the cured product of the curable composition is hard and brittle. Furthermore, the effect of substantially suppressing the inhibition of polymerization by oxygen and substantially eliminating the uncured product cannot be judged by a solid organic polymer (that is, the solid organic polymer has no liquid part in the first place). Therefore, even if the surface curability test is performed, it cannot be judged because the liquid material does not adhere to the surface of a finger or the like.) In the case of a liquid organic polymer, there is a problem that the surface becomes uncured.

JP 2014-31500 A

Accordingly, an object of the present invention includes an organic polymer that can significantly suppress inhibition of polymerization due to oxygen even when used in air to allow an appropriate curing reaction to proceed, and can ensure a degree of freedom in designing the composition. It aims at providing a curable composition and a product.

In order to achieve the above object, the present invention provides (A) an organic polymer having a group represented by the following general formula (1), (B1) a photoinitiator, (B2) a thermal initiator, and (B3). A curable composition is provided containing at least one initiator selected from the group consisting of redox initiators.

In the general formula (1), R ¹ represents —H or —CH ₃ , X represents a linking group, the linking group is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a polar linking group [( (Thio) ether linking group, —O—CO— linking group, —O—CO—NH— linking group, —NR ² — linking group (R ² is a hydrogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted An aryl group, a heterocyclic structure-containing group, or a group having a plurality of rings.)], Or a direct bond. In addition, this curable composition is obtained by reacting a polymer having a predetermined functional group with a functional group having reactivity to the predetermined functional group and a compound having a (meth) acrylate group (A). At least one initiation selected from the group consisting of an organic polymer having a group represented by the above general formula (1), (B1) a photoinitiator, (B2) a thermal initiator, and (B3) a redox initiator It can manufacture with the manufacturing method of the curable composition which mixes an agent and obtains a curable composition.

The curable composition can further contain (C) a monofunctional (meth) acrylic monomer.

In the curable composition, the (C) monofunctional (meth) acrylic monomer contains a (meth) acrylate containing a 3- (meth) acrylooxy 2-hydroxypropyl group and a polar group, -C _p H _2p It contains at least one monofunctional (meth) acrylic monomer selected from the group consisting of (meth) acrylates having an OH group (where p is an integer of 2 to 6) and alicyclic (meth) acrylates. Is preferred.

In the curable composition, (A) the main chain skeleton of the organic polymer having a group represented by the general formula (1) is a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer, Including at least one organic polymer selected from the group consisting of polyester polymers, polycarbonate polymers, graft polymers, hydrocarbon polymers, polysulfide polymers, polyamide polymers, and diallyl phthalate polymers You can also.

In the curable composition, the main chain skeleton of the organic polymer having a group represented by (A) the general formula (1) can also contain a polyoxyalkylene polymer.

In the curable composition, the main chain skeleton of the organic polymer having a group represented by (A) the general formula (1) can also contain a (meth) acrylic acid ester polymer.

In the curable composition, the (meth) acrylic acid ester polymer is a telechelic type organic polymer, a molecular terminal and functional group copolymer type organic polymer, and a terminal functional group type organic polymer. One organic polymer selected from the group consisting of

In the curable composition, the molecular terminal and functional group copolymer type organic polymer, or the terminal functional group type organic polymer is a polymer obtained by polymerizing a polymerizable monomer in the presence of a metallocene catalyst. There may be.

In the curable composition, the main chain skeleton of the organic polymer having a group represented by (A) the general formula (1) may include a polyester polymer.

Moreover, in the curable composition, the main chain skeleton of the organic polymer having the group represented by (A) the general formula (1) may include a polycarbonate polymer.

Moreover, in order to achieve the above object, the present invention provides a cured product of the curable composition described above.

Further, in order to achieve the above object, the present invention provides a product having a cured product of the curable composition described above as a constituent element.

According to the curable composition and product of the present invention, even when used in the air, it is possible to significantly suppress polymerization inhibition due to oxygen and to proceed with an appropriate curing reaction and to increase the degree of freedom in designing the composition. A curable composition containing an organic polymer that can be secured, and a product can be provided.

The curable composition according to the present invention comprises (A) an organic polymer having a group that suppresses polymerization inhibition by oxygen, (B1) a photoinitiator, (B2) a thermal initiator, and / or (B3) a redox initiation. Containing the agent. The curable composition may also contain (C) a monofunctional (meth) acrylic monomer.

Even if it is going to use the conventional monofunctional (meth) acrylate polymer as a component of a curable composition, the application to the adherend in the application where the curable composition is exposed and exposed to air, for example, a coating application or an adhesive application In coating and molding applications, the influence of polymerization inhibition due to oxygen is significant, and the curing reaction does not proceed properly. In addition, when it is desired to obtain a cured product having flexibility using a conventional monofunctional (meth) acrylate polymer, lauryl acrylate or the like is generally used, but in radical polymerization, polymerization inhibition occurs due to oxygen, The surface curability is insufficient.

Moreover, if a polyfunctional monomer is further added to the conventional curable composition together with the conventional monofunctional (meth) acrylate polymer, oxygen inhibition can be suppressed to some extent, but the cured product becomes hard, and the curved surface is bent. It cannot be used for applications where it is necessary to increase the coating thickness.

Therefore, the present inventor has studied various polymers to solve such a problem, and can solve the above-mentioned various problems by including an organic polymer having a group having a specific structure in the curable composition. It was found that polymerization inhibition by oxygen can be suppressed.

<(A) component: organic polymer>
Specifically, the curable composition according to the present invention contains (A) an organic polymer having a group represented by the following general formula (1) (hereinafter referred to as 3- (meth) acrylooxy 2-hydroxypropyl group). And (B1) a photoinitiator, (B2) a thermal initiator, and (B3) at least one initiator selected from the group consisting of redox initiators. The organic polymer as component (A) is liquid at normal temperature. Moreover, the curable composition may further contain (C) a monofunctional (meth) acrylic monomer.

In general formula (1), R ¹ represents —H or —CH ₃ , and X represents a linking group. Examples of the linking group include a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a polar linking group that is a polar group [(thio) ether linking group, —O—CO— linking group, —O—CO —NH— linking group, —NR ² — linking group (R ² represents a hydrogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a heterocyclic structure-containing group, or a group having a plurality of rings. And the linking group may be a direct bond. Here, the linking group is preferably a polar linking group from the viewpoint of suppressing polymerization inhibition by oxygen, more preferably —NR ² — linking group, —O—CO—NH— linking group, and —O—CO—NH. More preferred are linking groups.

The (thio) ether linking group represents an ether linking group [—O—] and / or a thioether linking group [—S—]. Also, “—O—CO— linking group” is “ester linking group”, “—O—CO—NH— linking group” is “urethane linking group”, and “—NR ² — linking group” is “amine linking group”. Called. Furthermore, in X of the general formula (1), the direct bond means that the polymer chain of the organic polymer is directly bonded to the carbon atom of the general formula (1) without a linking group.

[Mechanism to suppress inhibition of polymerization by oxygen]
The following formula is a schematic diagram for explaining a polymerization inhibition suppression mechanism by an organic polymer having a group represented by (A) the general formula (1). In the figure, “•” indicates a radical. In the figure, “(1)” indicates a hydrogen abstraction reaction, “(2)” indicates a polymerization initiation reaction, and “(3)” indicates an oxygen capture (consumption) reaction. Further, R ¹ is the same as described above, and a polymer chain is bonded after X.

The following mechanism is presumed as a mechanism for suppressing polymerization inhibition by oxygen. In other words, the polymerization inhibition by oxygen is caused by the fact that the polymerization ability of peroxyl radicals generated by trapping the oxygen radicals generated from the polymerization initiator and the polymerization end radicals generated from the polymerization initiator is low and the polymerization reaction is stopped. Occur. Here, when an organic polymer having a group represented by the general formula (1) having a function as a chain transfer agent is present in the system, a peroxy radical having a hydrogen abstraction ability is represented by the general formula (1). By extracting hydrogen from the group (reaction (1)), it is considered that the α-carbon radical of the newly generated secondary hydroxyl group starts polymerization (reaction (2)). In addition, since the α-carbon radical of the secondary hydroxyl group produced can supplement oxygen, the effect of reducing the oxygen concentration in the system (reaction (3)) is also conceivable. It is presumed that polymerization inhibition by oxygen is suppressed by these mechanisms. Further, even when the organic polymer having one group represented by the general formula (1) does not participate in the polymerization, the presence of the α carbon increases the opportunity for the polymerization reaction, so that the polymerization reaction is likely to proceed. .

Also, the carbon radicals are likely to be generated in the order of α-carbon of primary hydroxyl group <α-carbon of secondary hydroxyl group <α-carbon of secondary hydroxyl group to which a polar group is bonded. When the polar linking group is present in the general formula (1), the α-carbon radical of the secondary hydroxyl group is likely to be generated. Therefore, the group represented by the general formula (1) having the polar linking group is polymerized by oxygen. It has a more preferred structure in inhibiting inhibition.

The organic polymer having a group represented by the general formula (1) according to the present invention has a hydroxyl group. A compound having a hydroxyl group is hydrogen-bonded between molecules (that is, a hydrogen bond between hydroxyl groups or a hydrogen bond between a carbonyl group and a hydroxyl group). Therefore, the presence of the hydroxyl group increases local double bonds due to the association, so that the polymerization reaction easily proceeds.

[Main chain skeleton of organic polymer]
The polymer of the main chain skeleton of the organic polymer having a group represented by the general formula (1) is not particularly limited as long as it is an organic polymer having a group represented by the general formula (1). An organic polymer whose chain is not polysiloxane, and an organic polymer having various main chain skeletons excluding polysiloxane (that is, silicone) is preferable in that it does not contain or generate a low-molecular cyclic siloxane that causes contact failure. .

The weight average molecular weight of the organic polymer is preferably 1,000 or more, more preferably 2,000 or more, more preferably 3,000 or more in terms of polystyrene in GPC from the viewpoint of ensuring good elongation characteristics of the cured product of the curable composition. Further preferred. From the viewpoint of securing an appropriate viscosity of the curable composition and ensuring good workability, the weight average molecular weight is preferably about 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.

Further, (A) the organic polymer is preferably liquid at 50 ° C. That is, from the viewpoint of ensuring ease of handling when blended with other components, it is preferable to exhibit a liquid state at 50 ° C., more preferably a liquid state at 20 ° C., and a liquid state at 0 ° C. preferable.

Further, from the viewpoint of maintaining and improving the flexibility of the cured product of the curable composition, the glass transition temperature (Tg) is preferably 20 ° C. or less, more preferably 0 ° C. or less, and further preferably −10 ° C. or less. The organic polymer as the component (A) preferably has an A hardness after curing of less than 90, more preferably less than 85, and less than 80 from the viewpoint of maintaining and improving flexibility. Further preferred. In the description of the present invention, “having flexibility” means that the A hardness is less than 95. This A hardness is a value measured according to the test method of JIS K 7312 (1996), measured 30 seconds after the pressure surface of the type A durometer was brought into close contact with the cured product in a 23 ° C. atmosphere. In the component (A), X in the general formula (1) is preferably not —O—Arl— (wherein Arl is an arylene group).

Examples of the polymer of the main chain skeleton of the organic polymer having a group represented by the general formula (1) include polyoxypropylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and other polyoxypropylenes. Alkylene polymers; ethylene-propylene copolymers, polyisobutylene, polyisoprene, polybutadiene, hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; adipic acid Polyester polymer obtained by condensation of dibasic acid such as glycol and ring-opening polymerization of lactones; (meth) acrylic obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate Acid ester polymers; in main chain skeleton polymers such as polyoxyalkylene polymers Graft polymers obtained by polymerizing a vinyl monomer; polysulfide polymer; polyamide polymer; polycarbonate-based polymer; diallyl phthalate polymers. These skeletons may be contained alone in the organic polymer having the group represented by the general formula (1), or two or more kinds may be contained in blocks or randomly.

Among these, hydrocarbon polymers, polyoxyalkylene polymers, and (meth) acrylic acid ester polymers have a relatively low glass transition temperature, and the resulting curable composition has excellent cold resistance. Of these hydrocarbon polymers, saturated hydrocarbon polymers are preferred. Polyoxyalkylene polymers and (meth) acrylic acid ester polymers are particularly preferred because of their excellent flexibility.

(Polyoxyalkylene polymer)
The polyoxyalkylene polymer is a polymer having a repeating unit represented by the general formula (2).
-R ³ -O- (2)
In general formula (2), R ³ is a linear or branched alkylene group having 1 to 14 carbon atoms, preferably a linear or branched alkylene group having 1 to 14 carbon atoms, and having 2 to 4 carbon atoms. The linear or branched alkylene group is more preferable.

Repeating units of the polyoxyalkylene polymer represented by the general formula _{(2), -CH 2 CH 2} O in terms of flexibility after curing _{-, - CH 2 CH (CH} 3) O -, - CH 2 CH ₂ CH ₂ CH ₂ O- are _{preferable, -CH 2 CH (CH 3)} O -, - CH 2 CH 2 CH 2 CH 2 O- , more _{preferably, -CH 2 CH (CH 3)} O- is most preferable. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit or may be composed of two or more types of repeating units.

Examples of the method for synthesizing a polyoxyalkylene polymer include, but are not limited to, a polymerization method using an alkali catalyst such as KOH, for example, a polymerization method using a double metal cyanide complex catalyst, and the like. According to the polymerization method using a double metal cyanide complex catalyst, the number average molecular weight is 6,000 or more, the weight average molecular weight (Mw) / number average molecular weight (Mn) is a high molecular weight of 1.6 or less, and a polyoxyalkylene system having a narrow molecular weight distribution. A polymer can be obtained.

The main chain skeleton of the polyoxyalkylene polymer may contain other components such as a urethane bond component. Examples of the urethane bond component include aromatic polyisocyanates such as toluene (tolylene) diisocyanate and diphenylmethane diisocyanate; components obtained from a reaction between an aliphatic polyisocyanate such as isophorone diisocyanate and a polyoxyalkylene polymer having a hydroxyl group. Can be mentioned.

(Saturated hydrocarbon polymer)
The saturated hydrocarbon polymer is a polymer that does not substantially contain other carbon-carbon unsaturated bonds other than aromatic rings. The polymer forming the skeleton is either (1) polymerizing an olefinic compound having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene or isobutylene as a main monomer, or (2) a diene such as butadiene or isoprene. It can be obtained by a method such as homopolymerizing a system compound or copolymerizing a diene compound and an olefin compound and then hydrogenating. The isobutylene polymer and the hydrogenated polybutadiene polymer are preferable because it is easy to introduce a functional group at the terminal, easily control the molecular weight, and can increase the number of terminal functional groups, and the isobutylene polymer is particularly preferable. preferable. When the main chain skeleton is a saturated hydrocarbon polymer, the main chain skeleton has characteristics of excellent heat resistance, weather resistance, durability, and moisture barrier properties. Examples of the saturated hydrocarbon polymer include 1,2-polybutadiene, 1,4-polybutadiene, polyisoprene, and the like.

In the isobutylene polymer, all of the monomer units may be formed from isobutylene units, or may be a copolymer with other monomers. From the viewpoint of rubber properties, a polymer containing 50% by mass or more of repeating units derived from isobutylene is preferred, a polymer containing 80% by mass or more is more preferred, and a polymer containing 90 to 99% by mass is particularly preferred.

(Polyester polymer)
Polyester polymers can be obtained by various known methods. Typical methods include polybasic acids and polyhydroxy compounds, ε-caprolactone, β-methyl-δ-valerolactone, etc. It can be obtained by dehydration, dealcoholization reaction or addition reaction with one or more lactone monomers. For example, aliphatic dicarboxylic acids having 4 to 28 carbon atoms such as succinic acid, succinic anhydride, glutaric acid, adipic acid, and sebacic acid, and synergistic compounds of dicarboxylic acids such as dimethyl esters thereof, hexahydrophthalic anhydride, etc. As the acid component, there may be mentioned an alicyclic dicarboxylic acid, an aromatic dicarboxylic acid such as phthalic anhydride or its synergistic compound; a polybasic acid such as trimellitic anhydride and its synergistic compound. Of these, aliphatic dicarboxylic acids are preferred because the polyester polymer becomes flexible.

Examples of the polyhydroxy compound include linear diols such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butylene glycol, 1,6-hexanediol; 2-methyl-1,3-propanediol, 1,3- Branched diols such as butylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-butyl-2-ethyl-1,3-propanediol; cyclohexane Cyclic diols such as 1,4-dimethanol and spiroglycols; polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, lactone polyols, polycarbonate polyols, polyether polyols, polybutadiene polyols, or epoxies The fat and the like as the alcohol component. Moreover, the same effect component of the said polyhydroxy compound can also be used.

Of these, branched diols and cyclic diols are preferred, and branched diols are more preferred because the polyester polymer becomes flexible.

As the polyether polyol, for example, one or more of polyoxyethylene polyol, polyoxypropylene polyol, polyoxytetramethylene polyol, or ethylene oxide, propylene oxide, tetrahydrofuran, or the like obtained by polymerizing ethylene oxide, propylene oxide, tetrahydrofuran or the like alone And polyether polyols obtained by copolymerization of

In addition, the above-mentioned polyhydroxy compounds can be used as other polyols and synergistic components. These polyols can be used alone or in combination of two or more as required.

The polyester polymer is preferably a polyester polymer having no oxygen curable unsaturated group, and more preferably a saturated polyester polymer. A non-aromatic polyester polymer is preferable and a non-aromatic saturated polyester polymer is more preferable because the polyester polymer becomes flexible. From the viewpoint of ensuring application workability of the curable composition, the polyester polymer is preferably liquid at 50 ° C., more preferably liquid at 20 ° C., and most preferably liquid at 0 ° C.

((Meth) acrylic acid ester polymer)
Various monomers can be used as the (meth) acrylic acid ester monomer constituting the main chain of the (meth) acrylic acid ester polymer. For example, alkyl (meth) acrylate esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, etc. Monomer; Alicyclic (meth) acrylic acid ester monomer; Aromatic (meth) acrylic acid ester monomer; (Meth) acrylic acid ester monomer such as 2-methoxyethyl (meth) acrylate; γ- (methacryloyloxy) Propyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane and other silyl group-containing (meth) acrylate monomers; (meth) acrylic acid derivatives; fluorine-containing (meth) acrylate monomers Can be mentioned.

In the (meth) acrylate polymer, the following vinyl monomers can be copolymerized with the (meth) acrylate monomer. Examples of vinyl monomers include styrene, maleic anhydride, vinyl acetate and the like.

These may be used alone or may be copolymerized. Furthermore, the number of reactive functional groups in the (meth) acrylic acid ester polymer can be controlled by using the reactive functional group-containing (meth) acrylic acid ester monomer in combination. A methacrylic acid ester polymer comprising a methacrylic acid ester monomer is particularly preferred because of its good adhesion. In addition, when the viscosity is reduced, the flexibility is imparted, and the tackiness is imparted, it is preferable to use an acrylate monomer as appropriate. In addition, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

The method for producing the (meth) acrylate polymer is not particularly limited, and for example, a radical polymerization method using a radical polymerization reaction can be used. As the radical polymerization method, a radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator, or a functional group having reactivity at a controlled position such as a terminal can be introduced. Examples include controlled radical polymerization. However, a polymer obtained by a free radical polymerization method using an azo compound, a peroxide or the like as a polymerization initiator generally has a large molecular weight distribution value of 2 or more and a high viscosity. Therefore, in order to obtain a (meth) acrylate polymer having a narrow molecular weight distribution and low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high rate It is preferable to use a controlled radical polymerization method.

Examples of the controlled radical polymerization method include a free radical polymerization method and a living radical polymerization method using a chain transfer agent having a specific functional group. It is preferable to employ a living radical polymerization method such as an atom transfer radical polymerization method (Atom Transfer Radical Polymerization; ATRP). As a reaction for synthesizing a polymer whose main chain skeleton is a (meth) acrylic acid ester polymer and a part of which is a telechelic polymer (hereinafter referred to as “pseudo-telechelic polymer”), it is reactive. Reaction using a thiol compound having a functional group having a thiol compound, a reaction using a thiol compound having a reactive functional group, and a metallocene compound. The pseudo-telechelic polymer obtained by these reactions can also be used as long as it does not impair the function of the curable composition and the effect produced.

When obtaining a (meth) acrylate polymer having a hydroxyl group at one end, a reaction using a thiol compound having a hydroxyl group and a metallocene compound such as 2-mercaptoethanol described in JP-A No. 2000-344823 is used. A reaction using a compound having a thiol group and a secondary hydroxyl group such as thioglycerol (3-mercapto-1,2-propanediol) described in JP-A No. 2000-128911 can also be used.

(Polycarbonate polymer)
As a polycarbonate-type polymer, the reaction product of a carbonate and a polyol is mentioned, for example. Specific examples of the carbonate include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate. Dialkyl carbonate is preferred because the curable composition becomes flexible.

Examples of the polyol include the above-mentioned polyhydroxy compound and polyester polyol. In addition, as a polyester polyol, the polyester polyol (polyester polyol in which the polyhydroxy compound exists in the terminal) of the said polyester polymer can be used. As the polycarbonate, a non-aromatic polycarbonate is preferable because the curable composition becomes flexible.

[Polymer containing crosslinkable silicon group]
The main chain skeleton polymer may contain a crosslinkable silicon group. The crosslinkable silicon group is contained in the main chain skeleton polymer and / or at the terminal. That is, the component (A) can contain both a group represented by the general formula (1) and a crosslinkable silicon group. In this case, it is possible to improve adhesiveness and heat resistance by increasing the number of crosslinking points. In addition to curing of the group represented by the general formula (1) by photoreaction, thermal reaction, or redox reaction, the crosslinkable silicon group is further cured by moisture, so that the degree of curing of the cured product can be further increased. .

As the crosslinkable silicon group, for example, a group represented by the general formula (3) is preferable. The crosslinkable silicon group is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond.

In formula (3), R ⁴ represents an organic group. R ⁴ is preferably a hydrocarbon group having 1 to 20 carbon atoms. Among these, R ⁴ is particularly preferably a methyl group. R ⁴ may have a substituent. When two or more R ⁴ are present, the plurality of R ⁴ may be the same or different. W represents a hydroxyl group or a hydrolyzable group, and when two or more W exist, the plurality of W may be the same or different. a is an integer of 0, 1, 2, or 3. In view of curability, in order to obtain a curable composition having a sufficient curing rate, in formula (3), a is preferably 2 or more, more preferably 3. When using a curable composition as a photocurable composition, a is 2 from a viewpoint of obtaining the photocurable composition which has sufficient softness | flexibility.

Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different.

The hydrolyzable group represented by W is not particularly limited as long as it is other than an F atom, but an alkoxy group is preferable from the viewpoint of mild hydrolyzability and easy handling. From the viewpoint of high reactivity, a methoxy group or an ethoxy group is more preferable. The specific structure of the crosslinkable silicon group is preferably a trimethoxysilyl group or a triethoxysilyl group, and more preferably a trimethoxysilyl group from the viewpoint of high reactivity. From the viewpoint of obtaining a curable composition having sufficient flexibility, a methyldimethoxysilyl group and a methyldiethoxysilyl group are preferred.

[Synthesis Method of Organic Polymer]
The organic polymer of component (A) is a polymer having a functional group such as glycidyl group, carboxyl group, amino group, mercapto group, or isocyanate group in the molecule, glycidyl (meth) acrylate, (meth) acrylic acid, glycerin. It is obtained by reacting a functional group having reactivity with a functional group of a polymer such as mono (meth) acrylate and a compound having a (meth) acrylate group. For example, the organic polymer represented by the following general formula (I) is a predetermined polymer having a carboxyl group in glycidyl (meth) acrylate (R ¹ is the same as above) (-R ⁵ COOH, R ⁵ is substituted or An unsubstituted alkylene group, a substituted or unsubstituted arylene group, a heterocyclic structure-containing linking group, a linking group having a plurality of rings,-(C _m H _2m O) _n R ^β- (m is an integer of 2 to 4, n is an integer of 1-30, the R ^beta unsubstituted or substituted alkylene group, an unsubstituted or substituted arylene group), or show a direct bond.. "R ⁵ -." later is a polymer chain directly Bonding means directly bonding to a polymer chain.) Can be synthesized. For example, glycidyl (meth) acrylate, a predetermined carboxyl group-containing polymer and, if necessary, a predetermined catalyst are mixed in a predetermined solvent in a predetermined ratio, reacted at a predetermined temperature for a predetermined time, and the solvent is removed. Thus, the organic polymer represented by the general formula (I) is synthesized.

The organic polymer represented by the following general formula (II) is a predetermined polymer having an amino group in glycidyl (meth) acrylate (NHR ⁶ R ⁷ —, R ⁶ is —H, substituted or unsubstituted alkyl). A group, a substituted or unsubstituted aryl group, a heterocyclic structure-containing group, — (C _m H _2m O) _n R ^α (m, n, and R ^α are the same as described above), or a group having a plurality of rings .R ⁷ are the same as ^{R 5} - can be synthesized in the following is a polymer chain) reacting. ^{"R 7"..} For example, it is represented by the general formula (II) by mixing glycidyl (meth) acrylate, a predetermined amino group-containing polymer and a predetermined catalyst as required at a predetermined ratio and reacting at a predetermined temperature for a predetermined time. An organic polymer is synthesized.

In addition, an organic polymer represented by the following general formula (III) is reacted with a predetermined polymer having an isocyanate group on glycidol (O═C═N—R ⁷ —, R ⁷ is the same as described above). It can be synthesized by reacting the resulting intermediate reactant with (meth) acrylic acid. For example, an intermediate reaction product is synthesized by mixing a predetermined polymer having glycidol and an isocyanate group and a predetermined catalyst as required at a predetermined ratio and reacting at a predetermined temperature for a predetermined time. Then, the intermediate reactant obtained in this synthesis, a predetermined (meth) acrylate, and a predetermined catalyst as required are mixed at a predetermined ratio, and reacted at a predetermined temperature for a predetermined time, thereby allowing the general formula (III) Is synthesized.

In addition, during the synthesis reaction of the compound of the general formula (III), the epoxy group of glycidyl methacrylate is ring-opened to form an ester bond with the unsaturated carboxylic acid. This ring opening occurs at both the α-position and the β-position, but the α-adduct opened at the α-position is the main component, and the β-adduct opened at the β-position is the subcomponent. Usually, the production ratio of the α adduct and the β adduct is 100 / 0.01 to 100/70, preferably 100 / 0.1 to 100/50 in terms of molar ratio. In the synthesis reaction of the compound of the general formula (III), a product having a compound that is usually an α-adduct as a main component and a β-adduct as a subcomponent is obtained. When isolating the α-adduct that is the main component, the product can be isolated by separating it by a known separation method. In the synthesis reaction of the compound of the general formula (III), a mixture containing an α adduct and a β adduct is obtained. That is, the product obtained by the synthesis reaction of the compound of the general formula (III) is a product obtained by the above synthesis method in which all or part of the β adduct is left, and the α adduct is the main component. To do. Here, “main component” refers to a component contained in the product in an amount of 60 mol% or more, and “subcomponent” refers to a component contained in an amount of 40 mol% or less (the same applies hereinafter).

Therefore, in the synthesis reaction of the compound of the general formula (III), the α adduct is the main component and the β adduct is the subcomponent, so the organic polymer represented by the general formula (III) is converted into 3- (meta ) Urethane oligomer mainly containing acryloxy-2-hydroxypropyl group.

The organic polymer represented by the following general formula (IV) is a predetermined polymer having an isocyanate group in glycerin mono (meth) acrylate (O═C═N—R ⁷ —, R ⁷ is the same as described above. ) Can be synthesized. For example, a predetermined dihydroxy acrylate compound, a predetermined polymer having an isocyanate group, and a predetermined catalyst as required are mixed at a predetermined ratio, and reacted at a predetermined temperature for a predetermined time, and expressed by the general formula (IV). An organic polymer is synthesized. Here, in the synthesis reaction of the compound of the general formula (IV), only the α adduct is used. Therefore, the organic polymer represented by the general formula (IV) is substituted with a 3- (meth) acrylooxy 2-hydroxypropyl group. It is called a urethane oligomer.

Furthermore, the organic polymer represented by the following general formula (V) can be synthesized by reacting a predetermined (meth) acrylate and a predetermined polymer having a glycidyl group (R ⁸ is the same as X). . For example, it is represented by the general formula (V) by mixing a (meth) acrylate compound and a predetermined polymer having a glycidyl group and a predetermined catalyst as required at a predetermined ratio and reacting at a predetermined temperature for a predetermined time. An organic polymer is synthesized.

From the viewpoint that a predetermined polymer having a functional group is easily available, an organic polymer obtained by a reaction between a glycerin mono (meth) acrylate and a polymer having an isocyanate group, a reaction between a (meth) acrylate and a polymer having a glycidyl group And an organic polymer obtained by reacting glycidyl (meth) acrylate with a carboxyl group-containing polymer is preferred, an organic polymer obtained by reacting glycerin mono (meth) acrylate and a polymer having an isocyanate group, and ( An organic polymer obtained by a reaction between a meth) acrylate and a polymer having a glycidyl group is more preferable, and an organic polymer obtained by a reaction between a glycerin mono (meth) acrylate and a polymer having an isocyanate group is more preferable from the viewpoint of easy synthesis reaction. Most preferred.

(Regarding the number of functional groups in the organic polymer)
The organic polymer preferably has an average of 0.5 or more functional groups, more preferably 0.7 or more functional groups, from the viewpoint of increasing intermolecular crosslinking. More preferably 0.9 or more functional groups, and most preferably 1.0 or more functional groups. Moreover, the organic polymer preferably has 10 or less functional groups on average in one molecule from the viewpoint of increasing flexibility after curing, and more preferably has 5.0 or less functional groups. , More preferably 2.5 or less functional groups, and most preferably 2.0 or less functional groups.

(Reaction catalyst of glycidyl group and carboxyl group)
Catalysts for the addition reaction between carboxyl groups and epoxy groups include tertiary amines, quaternary ammonium salts, quaternary phosphonium salts, phosphine compounds such as triphenylphosphine, metal salts of carboxylic acids (eg chromium octoate, sodium stearate). Etc.), and alkali metal or alkaline earth metal hydroxides. Among these, it is preferable to use triphenylphosphine from the viewpoint that the resin is less colored, and from the viewpoint of good reaction yield, a metal salt of carboxylic acid, an alkali metal or alkaline earth metal hydroxide is preferable, and an alkali More preferred are metal or alkaline earth metal hydroxides, and even more preferred are alkali metal hydroxides. The catalyst for the addition reaction is preferably 0.01 equivalents or more and 0.1 equivalents or less, and more preferably 0.02 equivalents or more and 0.08 equivalents or less with respect to 1 equivalent of the epoxy group.

In the present invention, a polymerization inhibitor may be added from the viewpoint of suppressing radical polymerization during synthesis. Examples of the polymerization inhibitor include alkylphenols such as 2,6-di-t-butylhydroxytoluene. An amine polymerization inhibitor can also be used. Examples of the amine-based polymerization inhibitor include N, N′-diphenyl-p-phenylenediamine.

(Predetermined polymer having an isocyanate group)
Further, as the predetermined polymer having an isocyanate group used in the general formula (III) and the general formula (IV) (O═C═N—R ⁷ —, R ⁷ is the same as described above), for example, “general Reactive group-containing polymer having a predetermined main chain skeleton selected from the group consisting of “organic polymer having group represented by formula (1)” (hydroxyl group, carboxy group, and / or active hydrogen-containing amino group-containing organic group) Polymers) and isocyanate functional urethanes formed by reacting excess polyisocyanates can be used.

When the position of the reactive group of the reactive group-containing polymer having a predetermined main chain skeleton is the terminal (that is, when it does not exist in the main chain skeleton), the number of reactive groups is two from the viewpoint of flexibility after curing. One is preferable when flexibility is not particularly required. By using a polymer containing one reactive group and a polymer containing a large number of reactive groups, the hardness after curing can be designed freely. It is more preferred to use a polymer containing one reactive group and a polymer containing two reactive groups in combination.

Examples of the polyisocyanate include aliphatic isocyanates such as hexamethylene diisocyanate, tolylene diisocyanate, aromatic isocyanates such as 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, and alicyclic isocyanates such as isophorone diisocyanate, or These adduct types, isocyanurate types, burette types, and other multimers can be mentioned. The number of functional groups of polyisocyanate is preferably two from the flexibility after curing.

These organic polymers may be used alone or in combination of two or more. Specifically, an organic polymer obtained by blending two or more selected from the group consisting of a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth) acrylate polymer can also be used. .

Further, from the viewpoint of ensuring the flexibility of the cured product of the curable composition, a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer, a non-aromatic polyester polymer, and a non-aromatic polycarbonate polymer are preferable. , Polyoxyalkylene polymers and (meth) acrylic acid ester polymers are more preferred, and polyoxyalkylene polymers are more preferred.

[Organic polymer having a structure in which a functional group is introduced into the main chain skeleton polymer]
The component (A) is an organic polymer having a structure in which a functional group such as a glycidyl group, a carboxyl group, an amino group, a mercapto group, or an isocyanate group is introduced into the main chain skeleton polymer in the molecule, glycidyl (meth) acrylate, It can be synthesized by reacting a functional group having reactivity with a functional group of a polymer such as (meth) acrylic acid or glycerin mono (meth) acrylate, and a compound having a (meth) acrylate group. As an organic polymer having a structure in which a functional group is introduced into the main chain skeleton polymer, an organic polymer of “functional group copolymerization type” (shown in the following formula (a)) in which functional groups are randomly introduced, pieces Organic polymer of "one-end functional group type" (following formula (b)) having a functional group introduced at the terminal, "molecular terminal and functional group copolymerization type" (below Organic polymer of formula (c)), organic polymer of “multifunctionalization type of terminal functional group type” in which one terminal functional group type is linked with a polyfunctional monomer (formula (d) below), and main chain terminal There is an organic polymer of “telechelic type” (following formula (e)) into which a functional group is introduced. The formulas (a) to (e) are conceptual formulas of the structures of the respective polymers. In the formulas (a) to (e), X represents a functional group (for example, a carboxylic acid group, an amino group, Epoxy group, hydroxyl group, etc.), and when there are a plurality of X, they may be the same or different. In the expressions (a) to (e), n is a positive real number, and m is 0 or a positive real number. By controlling the position of the functional group introduced into the main chain skeleton polymer, the characteristics of the curable composition can be adjusted.

In the formula (a), the average number of functional groups is n. The organic polymer represented by the formula (a) preferably has an average functional group number of 10 or less, and an average functionality of 5.0 or less from the viewpoint of increasing the flexibility after curing. The number of functional groups is more preferable, the average number of functional groups is 2.5 or less, and the average number of functional groups is 1.1 or less. The organic polymer represented by the formula (a) preferably has an average functional group number of 0.5 or more in one molecule from the viewpoint of increasing intermolecular crosslinking, and has an average functionality of 0.7 or more. The number of groups is more preferable, the number of average functional groups of 0.9 or more is further preferable, and the number of average functional groups of 1.0 or more is most preferable.

In the formula (b), the number of functional groups is 1.

In both formula (c) and formula (d), the average number of functional groups is n + 1. In the formula (e), the average number of functional groups is m + n + 1. The organic polymers represented by formula (c), formula (d), and formula (e) all have an average number of functional groups in one molecule of 10 or less from the viewpoint of increasing flexibility after curing. Preferably, the average functional group number is 5.0 or less, more preferably 2.5 or less, still more preferably 2.0 or less. Most preferred. In addition, all of the organic polymers represented by the formula (c), the formula (d), and the formula (e) have an average functional group number of 1.1 or more per molecule from the viewpoint of increasing intermolecular crosslinking. Preferably, the average functional group number is 1.3 or more, more preferably 1.5 or more, still more preferably 1.8 or more. Most preferred.

The organic polymers represented by formula (a), formula (c), formula (d), and formula (e) are all (meth) acryl equivalent (number average per (meth) acryl group). The molecular weight) is preferably 1,000 or more, more preferably 2,000 or more, and still more preferably 3,000 or more from the viewpoint of ensuring good elongation characteristics of the cured product of the curable composition. In addition, from the viewpoint of securing an appropriate viscosity of the curable composition and ensuring good workability, the (meth) acryl equivalent is preferably about 100,000 or less, more preferably 50,000 or less, and 30,000 or less. Is more preferable.

Further, the (meth) acryl equivalent of the organic polymer represented by the formula (b) is preferably 500 or more, more preferably 1,000 or more, from the viewpoint of ensuring good elongation characteristics of the cured product of the curable composition. More preferably, 2,000 or more. Further, from the viewpoint of ensuring an appropriate viscosity of the curable composition and ensuring good workability, the (meth) acryl equivalent is preferably about 100,000 or less, more preferably 50,000 or less, and 30,000 or less. Is more preferable.

[(A) Copolymerization (b) Single terminal (c) Molecular terminal and copolymerization type]
The polymer of the “functional group copolymerization type” represented by the formula (a) can be synthesized relatively easily by copolymerizing a monomer having a functional group. From the viewpoint of increasing the number of functional groups in one molecule, a “functional group copolymerization type” polymer is effective. In addition, the “functional group copolymerization type” polymer has a short distance between the functional groups and may have a hard and brittle property. Moreover, the polymer of the “single terminal functional group type” represented by the formula (b) is an effective polymer when a functional group is introduced at the molecular terminal and flexibility after curing is required. It is also useful as a compatibilizing component. Moreover, the polymer of the “molecular end and functional group copolymerization type” represented by the formula (c) (the polymer represented by the formula (c) includes, for example, a functional group derived from acrylic acid in the main chain. , A one-end pseudo-telechelic polymer having a functional group at one end.) Is a polymer having the advantages of a one-end functional group type (formula (b)) and a functional group copolymerization type (formula (a)). It is. In addition, the polymer of “molecular end and functional group copolymerization type” can be combined with different functional groups in which the functional group at the molecular end is different from the functional group in the main chain. It can also be pursued.

[(D) Multimerization type of terminal functional group type]
Furthermore, the polymer of the “terminal functional group type multimerization type” represented by the formula (d) (the polymer represented by the formula (d) is, for example, a polymer having a single terminal functional group type as a polyfunctional monomer. ) Is useful as a crosslinking component, compatibilizing component, and thermosetting resin component due to the molecular structure having a plurality of highly reactive terminal functional groups and the multi-branched molecular structure. is there.

[(E) Telechelic type]
Taking a (meth) acrylic acid ester-based polymer as an example, a “telechelic type” polymer (formula (e)) is disclosed in, for example, Japanese Patent Application Laid-Open No. 2000-44626 and Japanese Translation of PCT International Publication No. 2013-523929. It can be synthesized by a living radical polymerization method in which the specific functional group described is introduced at the end of the main chain. When the living radical polymerization method is used, a telechelic type polymer having a functional group at the terminal can be produced by adding a low-polymerization olefin compound having a functional group during or after the polymerization. For example, a carboxylic acid group, ester group, ether group, hydroxyl group, epoxy group, amino group, amide group, silyl group and the like can be introduced.

In the atom transfer radical polymerization method, an organic halide or a sulfonyl halide compound is used as an initiator. By using an organic halide having a functional group or a sulfonyl halide compound in addition to the compound for initiating polymerization, a polymer having a functional group introduced at the terminal can be easily synthesized. Examples of such a functional group include a hydroxyl group, an epoxy group, and an amino group.

Further, for example, a free radical polymerization method using a chain transfer agent having a specific functional group described in JP-A No. 62-232408, or a thiol compound having a specific functional group described in JP-A No. 2000-344823 and A specific functional group can be introduced at one end by a reaction method using a metallocene compound. As an example, a part or all of the acrylic monomer and the functional group-containing mercaptan chain transfer agent are continuously supplied to the polymerization system, and the acrylic monomer is added to the acrylic monomer using a predetermined amount of the polymerization initiator. By carrying out radical polymerization, an acrylic polymer having a functional group at one end can be synthesized. The predetermined amount of the polymerization initiator is determined in consideration of the selectivity of the acrylic polymer having a functional group at one end. A “molecular end and functional group copolymerization type” can be synthesized by introducing a specific functional group into one end and then introducing the functional group into the main chain using a monomer having the specific functional group. Furthermore, a polymer having a terminal functional group type multimerization type can be synthesized by linking a polymer having a specific functional group introduced at one end with a polyfunctional monomer.

For example, ethyl acrylate (polymerizable monomer) is polymerized using ruthenocene (metallocene catalyst) and β-mercaptopropionic acid (polymerization initiator) as a metal catalyst described in Example 1 of JP-A-2000-344823. In addition to the method of synthesizing a propionic acid-terminated polymer, and the method of reacting a carboxy group-containing monomer such as acrylic acid as a polymerizable monomer, the molecular end (carboxy group) and functional group (carboxy group) copolymerization types are Synthesized. Further, for example, a terminal functional group (carboxy group) type multimerization (pseudotelephone) can be obtained by further reacting the polyfunctional monomer with the synthesis method described in Example 1 described in JP-A-2000-344823. Rick type) is synthesized. Note that β-mercaptopropionic acid is replaced with 2-mercaptoethanol described in Example 3 described in JP-A No. 2000-344823, and further, a method of reacting a hydroxyl group-containing monomer as a polymerizable monomer is used. Terminal (hydroxyl) and functional group (hydroxyl) copolymer types are synthesized. In addition, terminal functional group (hydroxyl) type multimerization (pseudo telechelic type) is synthesized by a method of reacting a polyfunctional monomer. Further, for example, even when a free radical polymerization method using a chain transfer agent having a specific functional group described in JP-A No. 62-232408 is used, theoretically the same molecular end and functional group copolymerization type, and A terminal functional group type multimerization can be synthesized, but a polymer using a metallocene catalyst is preferred because the terminal group generation probability is high (becomes a flexible polymer).

Note that a structure in which a functional group is introduced into the main chain skeleton polymer by random polymerization makes it difficult to obtain a flexible organic polymer because the distance between the functional groups is shortened. Moreover, since a molecule into which a functional group is not introduced is generated, a component that does not undergo radical polymerization is contained. Therefore, from the viewpoint of obtaining a flexible organic polymer, the structure in which a functional group is introduced into the main chain skeleton polymer includes “one-end functional group type”, “telechelic type”, “molecular end and functional group co-polymerization”. "Polymerization type" and "multimerization of terminal functional group type (pseudo-telechelic type)" are preferred, "one-end functional group type" and "telechelic type" are more preferred, and "telechelic type" is most preferred.

In the present invention, (B1) a photoinitiator, (B2) a thermal initiator, and / or (B3) a redox initiator are used as a polymerization initiator.

<(B1) component: Photoinitiator>
(B1) As the photoinitiator, a photoradical generator, a photobase generator, a photoacid generator, or the like can be used. The photo radical generator is a compound that generates radicals by irradiation with active energy rays such as ultraviolet rays and electron beams. In the curable composition of this invention, when (B1) photoinitiator is used as a polymerization initiator, since it can be used suitably also with respect to a heat-sensitive member, it can be used for various uses.

(Photo radical generator)
Examples of the photo radical generator include benzyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one. α-aminoacetophenone series, bis (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, etc. Acylphosphine oxides such as (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, benzophenones such as methyl benzoylbenzoate, thioxanthones such as isopropylthioxanthone, 1.2-octanedione, 1- [4- ( Oxime esters such as phenylthio)-, 2- (O-benzoyloxime)], bis (Cyclopentadienyl) -bis (2,6-difluoro-3- (pyrrol-1-yl) phenyl) titanium, titanocene, benzoin ether, triazine, borate, carbazole, imidazole, etc. Derivatives obtained by increasing the molecular weight thereof can be mentioned.

Of these, benzyl ketal, α-hydroxyacetophenone, α-aminoacetophenone, acylphosphine oxide, oxime ester, and titanocene photopolymerization initiators are preferred because they have high sensitivity and can be added in small amounts. , Α-aminoacetophenone-based, acylphosphine oxide-based, oxime ester-based, and titanocene-based photopolymerization initiators include long-wave ultraviolet rays (i-line (wavelength 365 nm), h-line (wavelength 405 nm), g-line (wavelength 436 nm), etc. ) Is more preferable because an LED light source can be used, and α-aminoacetophenone-based, acylphosphine oxide-based, and oxime ester-based photopolymerization initiators are most preferable because of their low sensitivity to visible light.

(Photobase generator)
Various photobase generators can be used as the photobase generator. Photolatent amine compounds that generate amine compounds by the action of active energy rays are preferred. The photolatent amine compound includes a photolatent primary amine that generates an amine compound having a primary amino group by the action of active energy rays, and an amine compound having a secondary amino group by the action of active energy rays. Any of the photolatent secondary amine that is generated and the photolatent tertiary amine that generates an amine compound having a tertiary amino group by the action of active energy rays can be used. In view of the high catalytic activity of the generated base, a photolatent tertiary amine is more preferable.

Examples of photolatent primary amines and photolatent secondary amines include orthonitrobenzylurethane compounds described in WO2015 / 088021, dimethoxybenzylurethane compounds, benzoins carbamates, o-acyloximes O-carbamoyl oximes; N-hydroxyimide carbamates; formanilide derivatives; aromatic sulfonamides; cobalt amine complexes and the like.

Examples of photolatent tertiary amines include α-aminoketone derivatives, α-ammonium ketone derivatives, benzylamine derivatives, benzylammonium salt derivatives, α-aminoalkene derivatives, α-ammonium alkene derivatives described in WO2015-088021. Amine imides, benzyloxycarbonylamine derivatives that generate amidine by light, and salts of carboxylic acids and tertiary amines. Among photobase generators, photolatent tertiary amines are preferred from the point that the generated bases exhibit high catalytic activity, because the base generation efficiency is high and the storage stability as a photocuring composition is good. Benzyl ammonium salt derivatives, benzyl substituted amine derivatives, α-amino ketone derivatives, and α-ammonium ketone derivatives are preferred.

When a photoinitiator is used, one kind may be used alone, or two or more kinds may be used in combination at any ratio. The addition amount of the photoinitiator is not particularly limited, but if the addition amount is small, the curing does not proceed to the deep part and the curing failure may occur. Therefore, “other than (A) component and (A) component is excluded. (Meth) acrylate "(however, other (meth) acrylates excluding component A include other (meth) acrylate monomers, oligomers, macromers, and / or components (C) other than component A). The same)) With respect to 100 parts by weight, 0.05 parts by weight or more is preferable, 0.1 parts by weight or more is more preferable, and 1 part by weight or more is still more preferable. In addition, if the initiator is large, the initiator may remain and adversely affect the cured properties, so the amount added is 100 parts by weight of “(A) component and other (meth) acrylates excluding component (A)”. On the other hand, it is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and still more preferably 10 parts by weight or less.

<(B2) component: thermal initiator>
Examples of (B2) thermal initiator used in the present invention include organic peroxides such as benzoyl peroxide, t-butyl perbenzoate and cumene hydroperoxide, 2,2′-azobisisobutyronitrile, And azo compounds such as 2,2′-azobis- (2-methylbutyronitrile) and 2,2′-azobis (2,4-dimethylvaleronitrile).

When using a thermal initiator (thermal polymerization initiator), one kind may be used alone, or two or more kinds may be used in combination at any ratio. The addition amount is not particularly limited, but from the viewpoint of storage stability, it is preferably 5 parts by weight or less, more preferably 100 parts by weight of (A) component and other (meth) acrylates excluding component (A). 2 parts by weight or less, more preferably 1 part by weight or less. Further, from the viewpoint of curability, it is preferably 0.01 parts by weight or more, more preferably 0.025 parts by weight or more, with respect to 100 parts by weight of other (meth) acrylates excluding the component (A) and the component (A). More preferably 0.05 parts by weight or more.

In the present invention, both (B1) photoinitiator and (B2) thermal initiator can be used together to achieve both photocuring and thermosetting.

<(B3) component: Redox initiator>
The redox initiator used in the present invention is not limited, but a combination of a persulfate initiator and a reducing agent (sodium metabisulfite, sodium bisulfite, thiourea compound, etc.); 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 an organic peroxide and a transition metal, or the like.

Preferred redox initiators include a combination of an organic peroxide and a tertiary amine, a combination of an organic peroxide and a transition metal, and more preferably a combination of cumene hydroperoxide and anilines, cumene. A combination of hydroperoxide and cobalt naphthate, a combination of cumene hydroperoxide and a trivalent or tetravalent vanadium compound, and the like can be given. A redox initiator may be used independently or may use 2 or more types together.

When using a redox initiator, the amount of addition is not particularly limited, but from the viewpoint of storage stability, it is preferably based on 100 parts by weight of the (A) component and other (meth) acrylates excluding the (A) component. It is 10 parts by weight or less, more preferably 5 parts by weight or less, and further preferably 2 parts by weight or less. Further, from the viewpoint of curability, it is preferably 0.01 parts by weight or more, more preferably 0.025 parts by weight or more, with respect to 100 parts by weight of other (meth) acrylates excluding the component (A) and the component (A). More preferably 0.05 parts by weight or more. Further, a curing accelerator such as an α-hydroxycarbonyl compound can be blended.

In the present invention, both (B1) photoinitiator and (B3) redox initiator can be used together to achieve both photocuring and redox curing.

<(C) component: monofunctional (meth) acrylate>
As the monofunctional (meth) acrylate, a (meth) acrylate containing a 3- (meth) acryloxyoxy-2-hydroxypropyl group and a polar group (the following general formula (4); hereinafter, (meth) in the general formula (4)) (Meth) acrylate represents acrylate and / or methacrylate), (meth) acrylates other than (meth) acrylates containing 3- (meth) acryloxyoxy-2-hydroxypropyl groups and polar groups ) A monomer having one acrylate group (hereinafter referred to as “monofunctional (meth) acrylate monomer” in the present description), or an organic polymer other than an organic polymer containing a 3- (meth) acryloxy-2-hydroxypropyl group. ) Polymer having one acrylate group (hereinafter referred to as “monofunctional (meth) acrylate polymer” It referred to as.) And the like.

((Meth) acrylate containing 3- (meth) acrylooxy 2-hydroxypropyl group and polar group)

In the general formula (4), R ¹ represents —H or —CH ₃ , and Y represents a polar group. Examples of the polar group include a phenoxy derivative group (—O—Ph—R ⁹ ₅ [Ph is a skeleton of a phenyl group], hereinafter referred to as “general formula (5)”), and an ester group (—O—CO—R ¹⁰ Hereinafter referred to as “general formula (6)”), (thio) ether group (—O—R ¹¹ and / or —S—R ^11, hereinafter referred to as “general formula (7)”), amine group ^(-NHpR _{12 2-p} [p is 0 or 1. hereinafter referred to as "the general formula (8)".]) and, urethane groups ^(-O-CO-NH-R 13. the following "general formula (9) ").

Here, in the general formula (5), five R ⁹ are bonded to Ph, and each of the plurality of R ⁹ independently represents a hydrogen atom or a substituent. Examples of the substituent include a nitro group, a cyano group, a hydroxy group, a halogen atom, an acetyl group, a carbonyl group, a substituted or unsubstituted allyl group, and a substituted or unsubstituted alkyl group (preferably having 1 to 5 carbon atoms). An alkyl group), a substituted or unsubstituted alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, a heterocyclic structure-containing group, and a plurality of rings. And a combination thereof. Any of a plurality of R ⁹ may be bonded to each other to form a cyclic structure. When at least two groups selected from the group consisting of a plurality of R ⁹ are bonded to each other to form a cyclic structure, a structure in which a plurality of benzene rings are condensed, a benzene ring and a heterocyclic ring, a non-aromatic ring, carbonyl A structure in which a ring or the like bonded to a functional group such as a group is condensed may be formed. Among these substituents, a substituted or unsubstituted alkyl group is preferable, and a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms is more preferable.

In general formula (6), general formula (7), general formula (8), and general formula (9), R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are substituted or unsubstituted alkyl groups, substituted or It represents an unsubstituted aryl group, a heterocyclic structure-containing group, a group having a plurality of rings, or a — (C _m H _2m O) _n R ¹⁴ group. In the general formula (8), when there are two R ¹² , the two R ¹² may be bonded to each other to form a cyclic structure or a heterocyclic structure together with the carbon atom to which they are bonded. Good. R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and / or R ¹³ may be a group having a silyl group. When the (meth) acrylate of the general formula (4) has a silyl group, the curable composition can be post-cured by moisture curing (so-called dual curing type).

Here, in the — (C _m H _2m O) _n R ¹⁴ group, m is an integer of 2 to 4, n is an integer of 1 to 30, R ¹⁴ is —H, or an unsubstituted or substituted alkyl group, unsubstituted Or it is a substituted phenyl group. Specifically, examples of ^{_{R 9, - (C m H}} 2m O) group ^{R 14} in the ^{n R 14} groups having a hydroxyl group _{H ;-( C m H 2m O)} R 14 in ^{n R 14} groups unsubstituted or group having an alkoxy group-substituted alkyl group ^{_{;-( C m H 2m O) R}} 14 in ^{n R 14} groups include groups having a phenoxy group unsubstituted or substituted phenyl group.

The substituted or unsubstituted alkyl group is not particularly limited, but for example, an alkyl group having 1 to 30 carbon atoms is preferable. In addition, the said alkyl group shall contain the alkyl group (broadly-defined alkyl group) containing the group which has a double bond. The substituted or unsubstituted aryl group is not particularly limited, but for example, an aryl group having 6 to 20 carbon atoms is preferable. Further, the substituted or unsubstituted alkyl group may be linear, branched or cyclic. In addition, the substituent in the substituted alkyl group and the substituted aryl group is not particularly limited, and examples thereof include a halogen atom, a hydroxyl group, an alkoxy group, an ester group, a ketone group, an aldehyde group, a carboxyl group, a glycidyl group, an amino group, and an amide. Groups and the like. The heterocyclic structure-containing group is not particularly limited, but for example, a heterocyclic structure-containing group having 3 to 20 carbon atoms is preferable. Further, the alkoxy group is not particularly limited, but an alkoxy group having 1 to 30 carbon atoms is preferable, and an alkoxy group having 1 to 18 carbon atoms is more preferable. Further, the ester group is preferably an ester group having 2 to 30 carbon atoms, and more preferably an ester group having 2 to 18 carbon atoms. As the ketone group, a ketone group having 2 to 30 carbon atoms is preferable, and a ketone group having 2 to 18 carbon atoms is more preferable.

Further, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and / or R ¹³ may be a group having a long chain hydrocarbon group having 8 to 20 carbon atoms, a carboximide group, or a crosslinkable silicon group. Good. From the viewpoint of excellent flexibility of the cured product of the curable composition, a long-chain hydrocarbon group having 8 to 20 carbon atoms and / or — (C _m H _2m O) _n R ¹⁴ group is preferable. Is more preferably a long chain hydrocarbon group having 8 to 20 groups, a group having a hydroxyl group or a group having an alkoxy group, and most preferably a long chain hydrocarbon group having 8 to 20 carbon atoms. From the viewpoint of curing the curable composition by a dual curing mechanism that also performs a curing reaction by moisture curing, a group having a crosslinkable silicon group is preferable.

Specific examples of R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and / or R ¹³ are as follows. First, examples of the group having a hydroxyl group include a 2-hydroxypropyl group, a 4-hydroxybutyl group, a hydroxyhexa (ethylene ether) group, a hydroxyocta (propylene ether) group, and a 2-hydroxy-3-butyloxypropyl group. It is done. Examples of the group having an alkoxy group include a methoxytri (ethylene ether) group, an ethoxydi (ethylene ether) group, and a dicyclopentenyloxyethyl group. Examples of the aromatic group include a phenoxyethyl group, a nonylphenoxyethyl group, and a benzyl group. Examples of the long-chain hydrocarbon (meth) acrylate group having 8 to 20 carbon atoms include 2-ethylhexyl group, isooctyl group, lauryl group, and isostearyl group. From the viewpoint of availability, the carbon number is 8-18 long chain hydrocarbon groups are preferred. Examples of the alicyclic group include a cyclohexyl group, a dicyclopentenyl group, and an isobornyl group. Examples of the group having a heterocyclic group include a tetrahydrofurfuryl group. Examples of the (meth) acrylate group having a crosslinkable silicon group include a 3- (trimethoxysilyl) propyl group, and the curable composition containing such a group undergoes a moisture curing reaction to form a dual curing mechanism. . A (meth) acrylate group having a crosslinkable silicon group is particularly effective as R ¹² .

(Monofunctional (meth) acrylate monomer)
Examples of the monofunctional (meth) acrylate monomer include the following compounds. First, as the long chain hydrocarbon (meth) acrylate having 8 to 20 carbon atoms, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, isostearyl (meth) acrylate, and the like are included. From the viewpoint of availability, long-chain hydrocarbon (meth) acrylates having 8 to 18 carbon atoms are preferable.

Examples of the alicyclic (meth) acrylate include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate.

Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, glycerol mono ( Hydroxyalkyl (meth) acrylates such as (meth) acrylate; polyalkylene glycol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polyethylene glycol-polypropylene glycol copolymers be able to.

Examples of the (meth) acrylate having an aromatic ring include benzyl (meth) acrylate, phenol alkylene oxide modified (meth) acrylate, alkylphenol alkylene oxide modified (meth) acrylate, p-cumylphenol alkylene oxide modified (meth) acrylate, and o -Phenylphenol alkylene oxide modified (meth) acrylate and the like. Examples of the alkylene oxide include ethylene oxide and propylene oxide.

Examples of alkoxy group-containing (meth) acrylates include alkoxy polyethylene glycol mono (meth) acrylates such as ethoxydiethylene glycol (meth) acrylate; alkoxypolypropylene glycol mono (meth) acrylates such as methoxytripropylene glycol (meth) acrylate; A polypropylene glycol copolymer etc. can be mentioned.

Examples of the (meth) acrylate having a carboxyl group include (meth) acrylic acid, modified polycaprolactone of (meth) acrylic acid, Michael addition type multimer of (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate and anhydrous Examples include adducts of phthalic acid and adducts of 2-hydroxyethyl (meth) acrylate and succinic anhydride.

Examples of the (meth) acrylate having a heterocyclic group include tetrahydrofurfuryl (meth) acrylate, N- (meth) acryloyloxyethyl hexahydrophthalimide, and the (meth) acrylate having an amino group includes N, N -Dimethylaminoethyl acrylate and the like.

Examples of the (meth) acrylate having a crosslinkable silicon group include 3- (trimethoxysilyl) propyl (meth) acrylate, and the (meth) acrylate having an epoxy group includes glycidyl (meth) acrylate and cyclohexene oxide. Examples of the (meth) acrylate having a phosphoric acid group include 2- (meth) acryloyloxyethyl acid phosphate. Moreover, the (meth) acrylate which has a fluoroalkyl group, the (meth) acrylate which has a tribromophenyl group, etc. are mentioned.

(Monofunctional (meth) acrylate polymer)
Moreover, a monofunctional (meth) acrylate polymer can be used. For example, an acrylic polymer having an acrylic polymer having one (meth) acryloyloxy group as a skeleton, a urethane (meth) acrylate polymer, a polyester (meth) acrylate polymer, a polyether (meth) acrylate polymer Examples thereof include an epoxy polymer and an epoxy (meth) acrylate polymer.

The weight average molecular weight of the polymer having one (meth) acrylate group is preferably 1,000 or more and 2,000 or more in terms of polystyrene in GPC from the viewpoint of securing good elongation characteristics of the cured product of the curable composition. More preferred is 3,000 or more. From the viewpoint of securing an appropriate viscosity of the curable composition and ensuring good workability, the weight average molecular weight is preferably about 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. The glass transition temperature (Tg) is preferably 10 ° C. or less, more preferably 0 ° C. or less, and further preferably −10 ° C. or less from the viewpoint of maintaining and improving the flexibility of the curable mucilage. Further, from the viewpoint of ensuring ease of handling when blended with other components, it is preferable to exhibit a liquid state at 50 ° C., more preferably a liquid state at 20 ° C., and a liquid state at 0 ° C. preferable.

Even if it is used in the air, it is less susceptible to polymerization inhibition by oxygen and has good curability. Therefore, (meth) acrylate of general formula (4), (meth) acrylate having a hydroxyl group, and alicyclic (meth) acrylate are preferable, (Meth) acrylate of general formula (4), (meth) acrylate having a hydroxyl group, and isobornyl (meth) acrylate are more preferable. (Meth) acrylate of general formula (4), 2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and isobornyl (meth) acrylate are more preferable. Most preferred is (meth) acrylate.

When considering the safety (explosion-proof viewpoint) of the obtained curable composition, it is desirable that the flash point of the curable composition is higher. Therefore, the flash point of monofunctional (meth) acrylate is preferably 60 ° C. or higher, and more preferably 70 ° C. or higher.

From the viewpoint of keeping the hardness of the cured product of the curable composition properly and exhibiting sufficient flexibility, the blending ratio of the monofunctional (meth) acrylate monomer is the same as the (meth) acrylate of the general formula (4), 10 mass parts or more are preferable with respect to 100 mass parts of functional (meth) acrylate monomers, 20 mass parts or more are more preferable, and 30 mass parts or more are the most preferable. From the viewpoint of exhibiting the effect of suppressing oxygen inhibition by the (meth) acrylate of the general formula (4) and exhibiting sufficient curability, the blending ratio of the monofunctional (meth) acrylate monomer is preferably 80 parts by mass or less, and 70 masses. Part or less is more preferable, and 60 parts by weight or less is most preferable.

In addition, from the viewpoint of exhibiting the inhibitory effect of oxygen inhibition by the organic polymer having a group represented by the general formula (1) and exhibiting sufficient curability, the blending ratio of the monofunctional (meth) acrylate polymer is: 80 parts by mass or less is preferable, 70 parts by mass or less is more preferable, and 60 parts by mass with respect to 100 parts by mass of the organic polymer having the group represented by the general formula (1) and the monofunctional (meth) acrylate polymer. The following are most preferred.

<Other additives>
The curable composition according to the present invention includes a vinyl-based copolymerizable with a polyfunctional (meth) acrylate monomer, a polyfunctional (meth) acrylate polymer, and an acrylate monomer as necessary or according to a curing method. Monomers, photosensitizers, photopolymerization accelerators, polymerization inhibitors, fillers, tackifying resins, silane coupling agents, extenders, diluents, plasticizers, moisture absorbers, curing catalysts, physical properties that improve tensile properties, etc. Various additives such as regulators, reinforcing agents, colorants, flame retardants, anti-sagging agents, antioxidants, anti-aging agents, UV absorbers, light stabilizers (HALS), solvents, fragrances, pigments, dyes, diluents, etc. May be added.

(Multifunctional (meth) acrylate monomer)
Polyfunctional (meth) acrylate monomers having two or more (meth) acryloyl groups include 1,6-hexadiol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) Acrylate, polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxytetraethoxyphenyl) propane, etc. Trifunctional (meth) acrylate monomer such as bifunctional (meth) acrylate monomer, trimethylolpropane tri (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, dimethylolpropane tetra (meth) acrylate, pentaerythritol Tetra ( Data) acrylate, or pentaerythritol ethoxy tetra (meth) acrylate 4 or more functional groups of the (meth) acrylate monomers.

(Polyfunctional (meth) acrylate polymer)
The polymer having a plurality of (meth) acrylate groups has two or more (meth) acryloyloxy groups other than (meth) acrylates containing 3- (meth) acrylooxy-2-hydroxypropyl groups and polar groups. A polyfunctional (meth) acrylate polymer can be used.

The weight average molecular weight of the polyfunctional (meth) acrylate polymer is preferably 1,000 or more, more preferably 2,000 or more in terms of polystyrene in GPC, from the viewpoint of ensuring good elongation characteristics of the cured product of the curable composition. More preferably 3,000 or more. From the viewpoint of securing an appropriate viscosity of the curable composition and ensuring good workability, the weight average molecular weight is preferably about 100,000 or less, more preferably 80,000 or less, and even more preferably 50,000 or less. The glass transition temperature (Tg) is preferably 10 ° C. or lower, more preferably 0 ° C. or lower, and further preferably −10 ° C. or lower, from the viewpoint of maintaining and improving the flexibility of the cured curable mucilage. Further, from the viewpoint of ensuring ease of handling when blended with other components, it is preferable to exhibit a liquid state at 50 ° C., more preferably a liquid state at 20 ° C., and a liquid state at 0 ° C. preferable.

Polyfunctional (meth) acrylate polymers include polyether-based urethane (meth) acrylates (eg, “UV-3700B” and “UV-6100B” manufactured by Nippon Gosei Co., Ltd.), polyester-based urethane (meth) acrylates (eg, Japan) “UV-2000B”, “UV-3000B”, “UV-7000B” manufactured by Synthetic Co., Ltd. “KHP-11”, “KHP-17” manufactured by Negami Kogyo Co., Ltd.), non-aromatic polycarbonate urethane (meth) acrylate (for example, “Art Resin UN-9200A” manufactured by Negami Kogyo Co., Ltd.), acrylic (meth) acrylate (for example, “RC-100C”, “RC-200C”, “RC-300C” manufactured by Kaneka Corporation), 1,2-polybutadiene Terminal urethane (meth) acrylate (for example, “TE-2000”, “TEA-10” manufactured by Nippon Soda Co., Ltd.) 0 "), 1,2-polybutadiene-terminated urethane (meth) acrylate hydrogenated product (for example," TEAI-1000 "manufactured by Nippon Soda Co., Ltd.), 1,4-polybutadiene-terminated urethane (meth) acrylate (for example, Osaka Organic Chemical Co., Ltd.) "BAC-45" manufactured by the company), polyisoprene-terminated (meth) acrylate, bisphenol A type epoxy (meth) acrylate, and the like.

(Vinyl monomer copolymerizable with acrylate monomer)
Examples of vinyl monomers copolymerizable with acrylate monomers include acrylic acid, methacrylic acid, acrylamide, acrylonitrile, methacrylonitrile, N-substituted acrylamide, hydroxyethyl acrylate, N-vinyl pyrrolidone, maleic acid, itaconic acid, Examples thereof include N-methylol acrylamide and hydroxyethyl methacrylate.

(Photosensitizer)
As the photosensitizer, a carbonyl compound having a triplet energy of 225 to 310 kJ / mol is preferable. For example, thioxanthone such as isopropylthioxanthone and derivatives thereof, dialkoxyanthracene derivative such as 9,10-dibutoxyanthracene, 2- Examples include benzophenone and its derivatives such as methyl benzoylbenzoate, and coumarin derivatives such as 3-acyl coumarin and 3,3'-carbonylbiscoumarin, thioxanthone and its derivatives and coumarin derivatives are preferred, thioxanthone and its derivatives, benzophenone and Its derivatives and coumarin derivatives are more preferred.

The mixing ratio of the photosensitizer is not particularly limited, but is preferably 0.01 to 5% by mass, more preferably 0.025 to 2% by mass in the curable composition. These photosensitizers may be used independently and may use 2 or more types together.

(Photopolymerization accelerator)
A photopolymerization accelerator can be used in combination with an initiator for the purpose of accelerating the curing reaction by the photopolymerization initiator. Photopolymerization accelerators include tertiary amines such as triethylamine, triethanolamine, 2-dimethylaminoethanol; aryl phosphines such as triphenylphosphine; aryl phosphine oxides such as triphenylphosphine oxide; triphenyl phosphite Phosphines including aryl phosphates such as triphenyl phosphate and the like (aryl groups may have a substituent); thiols typified by β-thioglycol and the like. Preferred phosphines are trifunctional phosphine derivatives, triarylphosphine is more preferred, and triphenylphosphine is most preferred.

(Polymerization inhibitor)
The polymerization inhibitor is not particularly limited. For example, radical scavengers such as hindered phenols and hindered amines, phosphorus secondary oxidative degradation inhibitors, diethylhydroxylamine, sulfur, t-butylcatechol, potassium triiodide, Examples thereof include N-nitrosophenylhydroxyamine aluminum salt. A polymerization inhibitor may be used independently and may use 2 or more types together.

If the content of the polymerization inhibitor is too small, the polymerization inhibitory effect tends to be insufficient, so that the (A) component and the (meth) acrylate other than the (A) component are 100 parts by weight. The amount is preferably 0.001 part by weight or more, more preferably 0.005 part by weight or more, and particularly preferably 0.01 part by weight or more. Moreover, since there exists a tendency for it to be inferior to curability when there is too much content of a polymerization inhibitor, 2 weight part or less is preferable, More preferably, it is 0.5 weight part or less, Most preferably, it is 0.3 weight part or less.

(Filler)
As the filler, a resin filler (resin fine powder), an inorganic filler, and a functional filler can be used. The filler may be subjected to a surface treatment with a silane coupling agent, a titanium chelating agent, an aluminum coupling agent, a fatty acid, a fatty acid ester, rosin or the like. As the resin filler, a particulate filler made of an organic resin or the like can be used. For example, as the resin filler, organic fine particles such as polyethyl acrylate resin, polyurethane resin, polyethylene resin, polypropylene resin, urea resin, melamine resin, benzoguanamine resin, phenol resin, acrylic resin, and styrene resin can be used. In addition, when using for the use as which the light-shielding property of the periphery part etc. of a liquid crystal display device is requested | required, it is preferable that a resin filler contains a black resin filler. Even when a single wavelength LED lamp or the like is used, good deep curability can be obtained, and excellent light shielding properties and deep curability can be achieved.

Examples of the inorganic filler include talc, clay, calcium carbonate, magnesium carbonate, anhydrous silicon, hydrated silicon, calcium silicate, titanium dioxide, and carbon black.

As the functional filler, for example, conductive fillers described in JP2013-14734, JP2017-2267, JP2011-508012, and the like; excellent heat insulation and lightness described in JP2016-199668, etc. Hollow particles; core-shell particles having excellent sound insulation and damping properties described in JP-A-2016-199669, etc .; layered silicates having excellent gas barriers described in JP-A-2016-199670, etc .; JP-A-2016-199671, etc. The light reflecting filler described in the above; the electromagnetic shielding material described in JP-A-2016-199750 and the like can be used.

(Diluent)
The curable composition of the present invention can contain a diluent. Here, a solvent having a flash point (open type) of 50 ° C. or higher is used as a diluent. By containing a diluent, physical properties such as viscosity can be adjusted. Various diluents can be used as the diluent. Diluents include, for example, saturated hydrocarbon solvents such as normal paraffin and isoparaffin, α-olefin derivatives such as linearlen dimer (trade name of Idemitsu Kosan Co., Ltd.), aromatic hydrocarbon solvents, alcohol solvents and ester solvents. Examples of the solvent include various solvents such as a solvent, a citrate ester solvent such as acetyltriethyl citrate, and a ketone solvent.

When considering the safety of the curable composition to be obtained, it is desirable that the curable composition has a high flash point, and it is preferable that the volatile material from the curable composition is small. Therefore, the flash point of the diluent is preferably 60 ° C. or higher, and more preferably 70 ° C. or higher. However, since a diluent generally having a high flash point tends to have a low dilution effect on the curable composition, it is preferable to use a diluent having a flash point of 250 ° C. or lower. In addition, when mixing 2 or more types of diluents, the flash point of a liquid mixture is said flash point.

When considering both safety and dilution effect of the curable composition of the present invention, the diluent is preferably a saturated hydrocarbon solvent, more preferably normal paraffin or isoparaffin. Normal paraffin and isoparaffin preferably have 10 to 16 carbon atoms.

The blending ratio of the diluent is preferably 0 to 50 parts by weight, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the (A) organic polymer. More preferably, it is blended in the range of 0.1 to 15 parts by mass. The diluent can be used alone or in combination of two or more.

In the present invention, the content of the liquid medium (volatile solvent, water) is preferably 5% by weight or less, more preferably 3% by weight or less, and more preferably 1% by weight or less based on the entire curable composition. More preferably, a composition containing substantially no liquid medium (that is, a substantially solvent-free composition) is most preferred. Here, “substantially does not contain” the liquid medium means that the curable composition does not contain any liquid medium or the content thereof is 0.1% by mass or less of the curable composition. Here, a solvent having a flash point of 50 ° C. or lower is used as a volatile solvent. For example, in a photocurable composition containing a liquid medium, it is preferable to irradiate active energy rays after drying the composition applied to the support.

<Method for producing curable composition>
There is no restriction | limiting in particular in the manufacturing method of a curable composition, For example, (A) component, (B1) component, and / or (B2) component are mix | blended with predetermined amount, and also (C) component and others as needed. It can manufacture by mix | blending these compounding substances and carrying out deaeration stirring. The order of blending each component and other compounding substances is not particularly limited and can be determined as appropriate. Moreover, a curable composition can also be made into 1 liquid type as needed, and can also be made into 2 liquid type.

<Photocurable composition>
A photocurable composition in which a curing reaction proceeds by photocuring includes (A) a curable composition containing an organic polymer having a group represented by the general formula (1), and the above-described curing initiator. (B1) a photoinitiator. Moreover, the photocurable composition may further contain a curing accelerator as necessary. The photocurable composition can be used in the air because the polymerization inhibition by oxygen can be significantly suppressed and an appropriate curing reaction can proceed. For example, the photo-curable composition of the present invention functions as a pressure-sensitive adhesive or an adhesive in air, since it can be temporarily fixed by adhesion immediately after light irradiation, and then moisture curing proceeds. Function as an adhesive).

Specifically, after a pressure-sensitive adhesive composed of a photocurable composition, or an adhesive is applied to the first adherend, and the photocurable composition is made to exhibit tackiness by direct light irradiation. In this state, the first adherend is bonded to the second adherend (temporarily fixed), and then the photocurable composition is moisture-cured to cure the first adherend and the second adherend. A product having a first adherend and a second adherend can be manufactured by bonding the adherend.

Also, for the coating agent and gasket, a polyfunctional monomer, polyfunctional oligomer, acrylamide, or the like is usually used in order to suppress polymerization inhibition by oxygen. However, these materials have hard cured properties, small elongation, and are not suitable for applications requiring flexibility. However, since the photocurable composition according to the present invention has a structure in which a functional group suppresses polymerization inhibition by oxygen, it can be widely used for applications requiring flexibility in addition to conventional applications. Moreover, since adhesiveness can also be provided to the photocurable composition of this invention, a photocurable composition can also be comprised as a coating agent and a gasket which have a softness | flexibility. Similarly, the photocurable composition can also be configured as a flexible paint, coating agent, ink, gasket, packing, O-ring, sealing agent, potting agent, casting material, sealing agent, and the like.

(When the photocurable composition contains a crosslinkable silicon group)
In addition, when the organic polymer having the group represented by (A) the general formula (1) is a compound containing a crosslinkable silicon group, a moisture curing method can be used in combination. In this case, the photocurable composition preferably contains a photobase generator as a curing initiator. In addition, a silicon compound having a Si—F bond can be added as a curing accelerator. Since the component (A) contained in the photocurable composition has a crosslinkable silicon group, after the photocurable composition is photocured, the photocurable composition can be postcured by moisture in the air. .

As the silicon compound having a Si—F bond, various compounds containing a silicon group having a Si—F bond (hereinafter sometimes referred to as a fluorosilyl group) can be used. Either an inorganic compound or an organic compound can be used as the silicon compound having a Si—F bond. As the silicon compound having a Si—F bond, an organic compound having a fluorosilyl group is preferable, and an organic polymer having a fluorosilyl group is more preferable because of high safety. Moreover, the low molecular organosilicon compound which has a fluoro silyl group from the point from which a photocurable composition becomes low viscosity is preferable.

Examples of silicon compounds having a Si—F bond include fluorosilanes described in WO2015-088021, compounds having a fluorosilyl group described in WO2015-088021, and fluorosilyls described in WO2015-088021 And an organic polymer having a group.

<Thermosetting composition>
The thermosetting composition in which the curing reaction proceeds by heat includes (A) a curable composition containing an organic polymer having a group represented by the general formula (1), and the above-described curing initiator. (B2) contains a thermal initiator. Moreover, the thermosetting composition may further contain a curing accelerator as necessary. Moreover, the thermosetting composition with favorable workability (low viscosity) is obtained by using together with the (meth) acrylate shown by General formula (4) which can suppress the superposition | polymerization inhibition by oxygen significantly.

The thermosetting composition can be used for various purposes. In particular, the thermosetting composition of the present invention can be suitably used in the presence of air because it can greatly suppress inhibition of polymerization due to oxygen and can promote an appropriate curing reaction. For example, the thermosetting composition of the present invention can be used for LIM molding in which the influence of oxygen in the air cannot be excluded, and can be widely used for applications requiring flexibility in addition to conventional applications. . Moreover, since adhesiveness can also be provided to the thermosetting composition of this invention, it is suitable for insert LIM shaping | molding (LIM insert vulcanization adhesion shaping | molding).

Examples of the initiator used in the thermosetting composition for LIM molding include a radical initiator having a half-life of 0.5 to 120 seconds, preferably 1 to 60 seconds, at any reaction temperature between 130 and 160 ° C. It is done. In the case of an initiator having a half-life exceeding 120 seconds, the fluctuation range of the monomer conversion rate becomes large and it is difficult to ensure stable operation. In the case of an initiator having a half-life of less than 0.5 seconds, there is a problem that the amount of the initiator used is too large and the product polymer is colored. Examples of the initiator used in the present invention include 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (2-methylbutyronitrile), and the like. Preferred are azo compounds and organic peroxides such as 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, t-butyl peroxyisobutyrate, benzoyl peroxide, lauroyl peroxide. In the present invention, the half-life value of the initiator is the value of technical bulletin issued by Wako Pure Chemical Industries, Ltd. for azo compounds, and the catalog (12th edition) issued by Nippon Oil & Fats Co., Ltd. for organic peroxides. Is adopted. The polymerization reaction temperature in the LIM molding step is preferably in the range of 100 to 180 ° C, more preferably in the range of 130 to 160 ° C, and still more preferably in the range of 140 to 155 ° C.

<Redox curable composition>
The redox curable composition in which curing proceeds by a redox reaction includes (A) a curable composition containing an organic polymer having a group represented by the general formula (1), and the above-described curing initiator. (B3) contains a redox initiator. Moreover, the redox curable composition may further contain a hardening accelerator as needed. The redox curable composition can be used for various applications for the same reason as the photocurable composition.

(A) A redox curable composition containing an organic polymer having a group represented by the general formula (1) can be used as a two-component mixed adhesive in the air. For example, a first liquid containing a persulfate initiator or an organic peroxide, a component (A) or a component (C), a reducing agent, a tertiary amine, or a transition metal, and a component (A) Alternatively, by using a second liquid containing component (C) and the like, a two-component mixed adhesive can be configured. Since the reaction proceeds by mixing the first liquid and the second liquid, it functions as an adhesive that bonds one adherend and the other adherend together. The component (A) is contained in at least one of the first liquid and the second liquid. In addition, as described in the section of the redox initiator which is the component (B3), the combination of the compound contained in the first liquid and the compound contained in the second liquid is a combination of a persulfate initiator and a reducing agent. A combination of an organic peroxide and a tertiary amine, a combination of an organic peroxide and a transition metal, or the like can be appropriately employed.

Specifically, for example, as described in JP2013-111701, the first liquid contains an organic peroxide, an acidic phosphate ester (storage stability improver), an α-hydroxycarbonyl compound (a curing accelerator). Agent), hydrazine compound (aldehyde emission inhibitor), etc., and the second liquid is a reducing agent such as trivalent or tetravalent vanadium compound, thiourea compound, saccharin, aluminum compound (storage stability) Improver) and the like, and a stabilizer such as disubstituted hydroquinone can be added to the first liquid and / or the second liquid. In addition, when making the redox curable composition of this invention into a primer type, reducing agents, such as a vanadium compound and a thiourea compound, can be dissolved and used in a volatile solvent.

Also, adhesives, coating agents, and gaskets usually use polyfunctional monomers, polyfunctional oligomers, acrylamide, or the like in order to suppress polymerization inhibition by oxygen. However, these materials have hard cured properties, small elongation, and are not suitable for applications requiring flexibility. However, since the redox curable composition according to the present invention has a structure in which a functional group suppresses the inhibition of polymerization by oxygen, it can be widely used for applications requiring flexibility in addition to conventional applications. The product can be configured as a flexible adhesive, a coating agent or a gasket, or a pressure-sensitive adhesive for applications requiring flexibility. Adhesives, pressure sensitive adhesives, coating agents and gaskets are particularly useful for field construction. Similarly, redox curable compositions can also be configured as flexible paints, coating agents, inks, gaskets, packings, O-rings, sealing agents, potting agents, casting materials, sealants, etc. Useful for construction. The redox curable composition of the present invention can also be used for two-component curable LIM molding.

<Products having cured products of curable compositions as constituent elements>
The curable composition according to the present invention is cured by photocuring, heat curing, and / or redox curing. By this curing, a cured product of the curable composition can be obtained. Therefore, various products, such as an electronic circuit, an electronic component, a building material, and a motor vehicle, can be manufactured using the hardened | cured material of a curable composition. For example, a product can be manufactured by apply | coating the curable composition which concerns on this invention to a predetermined to-be-adhered body, and making it harden | cure.

The curable composition of the present invention can suppress the polymerization inhibition due to oxygen even when used in the air, and can proceed with an appropriate curing reaction, and becomes a flexible cured product. Suitable. That is, the curable composition of the present invention is applied to an adherend and cured in situ, or the curable composition of the present invention is applied in a predetermined shape (for example, a ring shape used for packing or gasket), By curing, a ring-shaped packing or gasket can be manufactured on the spot. Here, in the present invention, “for on-site construction” means that the curable composition is used as it is (in the air) for adhering adherends to each other and for producing a member having a predetermined shape at the site where the product is manufactured. Point to. For example, “for on-site construction” is an application in which a curable composition is directly applied to one adherend, and in that state (or on the spot), one adherend is attached to the other adherend; And / or the use etc. which manufacture the product which has the said shape by making a curable composition into a predetermined shape and hardening.

Specifically, the curable composition of the present invention includes a pressure-sensitive adhesive, an adhesive, an elastic adhesive, a contact adhesive, a coating material, a coating material, a sealing material such as a can lid, an electric and electronic potting agent, a film, and a gasket. , Marine deck caulking, casting materials, various molding materials, anti-rust / waterproof sealing materials for meshed glass and laminated glass end faces (cutting parts), anti-vibration / damping / Liquid and sealing materials used in soundproofing and seismic isolation materials, automobile parts, electrical parts, various machine parts, waterproofing agents, sealing materials for double-glazed glass, sealing materials for vehicles, such as architectural and industrial sealing agents, solar cells It can be used for various applications such as electrical / electronic component materials such as backside sealants, and electrical insulation materials such as insulation coating materials for electric wires and cables.

Also, the on-site molded body showing rubber elasticity composed of the curable composition of the present invention can be widely used mainly for gaskets and packings. For example, in the automobile field, it can be used as a body part as a sealing material for maintaining airtightness, an anti-vibration material for glass, an anti-vibration material for vehicle body parts, particularly a wind seal gasket and a door glass gasket. In the field of home appliances, it can be used for on-site packing, O-rings, and the like. Specifically, decorations for lighting fixtures, waterproof packings, anti-vibration rubbers, insect-proof packings, anti-vibration / sound absorption and air sealing materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater unit packings , Electrode packing, waterproof packing for smartphones, solenoid valve, waterproof packing for steam microwave oven and jar rice cooker, water tank packing, water absorption valve, water receiving packing, heat insulation heater packing, steam outlet seal, etc. Examples include oil gaskets, O-rings, drain packings, feed / intake packings, anti-vibration rubbers, oil filler packings, oil meter packings, speaker gaskets and speaker edges for acoustic equipment. In the construction field, it can be used for gaskets, waterproof materials, vibration-proof materials, sound-proof materials, and the like. In the DIY field, it can be used for shoe sole repair materials, insole repair materials, and the like. In the field of anti-vibration rubber, it can be used for anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, and the like.

Among these, the curable composition of the present invention is particularly useful as a pressure-sensitive adhesive or an adhesive, and is particularly useful for applications requiring on-site construction. In addition, since the curable composition of the present invention can be configured as a cured product having good flexibility, it is an elastic adhesive used for bonding materials having different linear expansion coefficients to each other or a member that repeatedly undergoes displacement by heat cycle. It is also useful for applications such as coating agents for bending members that utilize flexibility and flexibility. Moreover, it can also be suitably used for a liquid sealing material used in on-site molded gaskets, so-called automobile parts, electrical parts, various machine parts, etc., taking advantage of its good surface curability.

Among the above applications, it is particularly useful for adhesives for electric and electronic devices, pressure sensitive adhesives, sealing materials, potting agents, packings, coating materials and the like.

<Effect of Embodiment>
Since the curable composition according to the present invention contains (A) an organic polymer having a group represented by the general formula (1), the polymerization inhibition due to oxygen can be greatly suppressed even when used in the air, and appropriate. A cured product having excellent curability can be obtained. Moreover, the curable composition which concerns on this invention can select various coupling groups as X of General formula (1), and it connects with group represented by General formula (1) through a coupling group. Since various skeletons can be selected as the main chain skeleton of the polymer to be cured, it is possible to ensure a wide range of design freedom of the curable composition from which the cured product is obtained (that is, physical properties such as hardness of the cured product) The degree of freedom of design can be secured, and the physical properties can be selected according to the purpose of using the cured product. Furthermore, since the curable composition is excellent in compatibility, various compounds can be added as long as the effects of the invention are not impaired.

More specific description will be given below with reference to examples. Needless to say, these examples are illustrative and should not be interpreted in a limited manner.

(Synthesis Example 1) Polymer A
Carboxyl group-containing acrylic polymer 10.0 g (product name “Actoflow CB-3098”, manufactured by Soken Chemical Co., Ltd., molecular terminal and functional group copolymerization type poly-2-ethylhexyl acrylate, weight average molecular weight = 3,000, AV = 98 ± 1), 2.48 g of equimolar equivalent of glycidyl methacrylate, 0.009 g of TPP (triphenylphosphine) as a catalyst, and 10.0 g of ethyl acetate as a solvent were added and reacted at 70 ° C. for 24 hours. After the reaction, ethyl acetate was distilled off under reduced pressure. As a result of IR spectrum measurement of the produced polymer A at room temperature, it was confirmed that an —OH stretching (broad, 3,200 to 3,500 cm ⁻¹ ) peak caused by glycidyl group ring opening occurred. . In addition, the average number of functional groups contained in polymer A was 2.3 per molecule (however, 1.0 at the end and 1.3 per molecule).

During the above synthesis reaction, the epoxy group of glycidyl methacrylate is ring-opened to form an ester bond with the unsaturated carboxylic acid. This ring opening occurs at both the α-position and the β-position, but the α-adduct opened at the α-position is the main component, and the β-adduct opened at the β-position is the subcomponent. Usually, the production ratio of the α adduct and the β adduct is 100 / 0.01 to 100/70, preferably 100 / 0.1 to 100/50 in terms of molar ratio. In Synthesis Example 1, a product having a compound that is usually an α-adduct as a main component and a β-adduct as a subcomponent is obtained. The α-adduct as the main component can be separated and isolated from the product by a known separation method. In Synthesis Example 1, a mixture containing an α adduct and a β adduct is obtained as the polymer A. That is, the product obtained in Synthesis Example 1 is a product obtained by leaving the whole or part of the β adduct in the product obtained by the above synthesis method, and is a curable composition containing the α adduct as a main component. .

(Synthesis Example 2) Polymer B
Polyoxypropylene diamine 10 g (product name “JEFFAMINE D2000”, manufactured by Huntsman Corporation, weight average molecular weight = 2,000) and equimolar equivalent of glycidyl methacrylate 2.84 g, accelerator 399 0.3 g (manufactured by Huntsman Corporation) In addition, the mixture was reacted at 70 ° C. for 24 hours. As a result of IR spectrum measurement of the produced polymer B at room temperature, it was confirmed that an —OH stretching (broad, 3,200 to 3,500 cm ⁻¹ ) peak due to ring opening of the glycidyl group occurred. Polymer B contains functional groups at both ends.

(Synthesis Example 3) Polymer C
Add 0.46 g of glycidol (product name “Epiol OH”, manufactured by NOF Corporation) to 10.0 g of urethane prepolymer (weight average molecular weight = 3,500) having a PTMG (polytetramethylene ether glycol) skeleton. , And reacted at 70 ° C. for 48 hours. As a result of IR spectrum measurement of the product, it was confirmed that absorption of —NCO derived from isocyanate group disappeared. To the obtained product, 0.43 g of acrylic acid (manufactured by Mitsubishi Rayon Co., Ltd.) and 0.007 g of TPP as a catalyst were added and reacted at 70 ° C. for 24 hours. As a result of IR spectrum measurement of the produced polymer C at room temperature, it was confirmed that an —OH stretching (broad, 3,200 to 3,500 cm ⁻¹ ) peak caused by glycidyl group ring opening was generated. Polymer C contains functional groups at both ends.

(Synthesis Example 4) Polymer D
0.47 g of equimolar equivalent of glycidol was added to 10.0 g of urethane prepolymer having a PPG (polypropylene glycol) skeleton (weight average molecular weight = 3,000), and reacted at 70 ° C. for 48 hours. As a result of IR spectrum measurement of the product, it was confirmed that absorption of —NCO derived from isocyanate group disappeared. To the obtained product, 0.46 g of equimolar equivalent acrylic acid and 0.01 g of TPP as a catalyst were added and reacted at 70 ° C. for 24 hours. Result of IR spectra of the polymer D of the liquid in the generated normal temperature, it was confirmed that -OH stretch (broad, 3,200 ~ 3,500cm ^-1) due to the glycidyl group ring opening peak has occurred. Moreover, the polymer D contains a functional group at both ends.

(Synthesis Example 5) Polymer E
An equimolar equivalent of 1.01 g of glycerol monomethacrylate was added to 10.0 g (weight average molecular weight = 3,000) of a urethane prepolymer having a PPG skeleton, and reacted at 70 ° C. for 24 hours. As a result of IR spectrum measurement of the produced polymer E at room temperature, it was confirmed that absorption of —NCO derived from isocyanate group disappeared. Polymer E contains functional groups at both ends.

The polymer obtained in Synthesis Example 1 is an organic polymer represented by the general formula (I) described in the embodiment, Synthesis Example 2 is an organic polymer represented by the general formula (II), and Synthesis Examples 3 to 4 are used. Corresponds to the organic polymer represented by the general formula (III), and Synthesis Example 5 corresponds to the organic polymer represented by the general formula (IV).

(Synthesis Example 6) Polymer F
Hydroxyl group-containing oligomers (PBA1; number average molecular weight 10,000, primary and secondary at one end) of n-butyl acrylate (BA) skeleton obtained by reaction using thioglycerol described in JP-A No. 2000-128911 There is one hydroxyl group each). 100 g of xylylene diisocyanate (XDI) is reacted with 3.8 g of xylene diisocyanate (XDI). 3.7 g of methacrylate and 0.05 g of a polymerization inhibitor (hydroquinone) were added and reacted at 70 ° C. for 24 hours. The number average molecular weight was 22,000, and the liquid 2-hydroxypropyl methacrylate group was liquid at room temperature. Thus, a urethane acrylate (polymer F) having two BA skeletons was obtained. As a result of IR spectrum measurement, it was confirmed that absorption of —NCO derived from an isocyanate group disappeared and absorption of —OH stretching derived from a hydroxyl group remained. The number average molecular weight is a polystyrene equivalent molecular weight measured by gel permeation chromatography using Tosoh's HLC-8120GPC as the liquid feeding system, the column using Tosoh's TSK-GELH type, and the solvent using THF.

(Synthesis Example 7) Polymer G
A urethane prepolymer having a PPG skeleton at both ends of an isocyanate group, obtained by reacting 4.0 g of xylylene diisocyanate (XDI) with 100 g of PPG (polypropylene glycol, Mw / Mn = 1.1, number average molecular weight: 10,000) (PU-PPG10000) 3.9 g of glycerol monomethacrylate and 0.05 g of a polymerization inhibitor (hydroquinone) are added to 104.0 g and reacted at 70 ° C. for 24 hours. The number average molecular weight is 32,000 and is liquid at room temperature. A urethane acrylate (polymer G) having a PPG skeleton at both ends of 2-hydroxypropyl methacrylate was obtained. As a result of IR spectrum measurement, it was confirmed that absorption of —NCO derived from an isocyanate group disappeared and absorption of —OH stretching derived from a hydroxyl group remained.

(Synthesis Example 8) Polymer H
PTGM (polytetramethylene ether glycol, number average molecular weight = 2,000) obtained by reacting 18.8 g of xylylene diisocyanate (XDI) with 118.8 g of a urethane prepolymer having a PTMG skeleton at both ends of the isocyanate group 16 g of monomethacrylate and 0.05 g of a polymerization inhibitor (hydroquinone) were added and reacted at 70 ° C. for 24 hours. The number average molecular weight was 2,800, and liquid PTGM at both ends of the 2-hydroxypropyl methacrylate group at room temperature. A skeleton urethane acrylate (polymer H) was obtained. As a result of IR spectrum measurement, it was confirmed that absorption of —NCO derived from an isocyanate group disappeared and absorption of —OH stretching derived from a hydroxyl group remained.

Synthesis Example 9 Monomer B
An equimolar amount of 5.00 g of glycidyl methacrylate and 0.09 g of TPP as a catalyst were added to 10.0 g (35.2 mmol; manufactured by Nissan Chemical Industries, Ltd.) of isostearic acid and reacted at 70 ° C. for 8 hours. As a result of IR spectrum measurement of the produced monomer B, it was confirmed that absorption of —OH stretching (broad, 3,300 to 3,500 cm ⁻¹ ) derived from carboxylic acid disappeared. Then, it was confirmed that -OH stretch (broad, 3,200 ~ 3,600cm ^-1) due to the glycidyl group ring opening peak has occurred.

(Comparative Synthesis Example 1) Polymer A ′: Synthesis example of poly (acrylic acid n-butyl acrylate) at both terminals of acryloyl group Cuprous bromide as catalyst, pentamethyldiethylenetriamine as ligand, diethyl-2,5-dibromoadipate Using n-butyl acrylate as a monomer and potassium acrylate as an end group introducing agent, and a reaction according to the method of Synthesis Example 2 described in WO2008 / 041768, and the number average in terms of polystyrene. A polymer A ′ which is a poly (acrylic acid-n-butyl) polymer having a molecular weight of 20,000, an average number of acryloyl groups of about 1.9 per molecule, and acryloyl groups at both ends at room temperature. Obtained.

(Comparative Synthesis Example 2) Polymer B ′: Synthesis example of poly (poly (n-butyl acrylate) / ethyl acrylate / 2-methoxyethyl acrylate) at both terminals of acryloyl group Cuprous bromide as catalyst and pentamethyldiethylenetriamine as ligand Diethyl-2,5-dibromoadipate as an initiator, n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate in a mole ratio of 25/46/29 as a monomer, and potassium acrylate as a terminal group Used as an introducing agent, the reaction was carried out in accordance with the method of Synthesis Example 4 described in WO2007 / 029733, and the number average molecular weight was 20,000 in terms of polystyrene, and the number of acryloyl groups was about 1.8 per molecule on average. Poly (n-butyl acrylate / ethyl acrylate / 2-methoxy) having acryloyl groups at both ends Chill acrylate) was at room temperature a polymer to obtain a polymer B 'of the liquid.

(Comparative Synthesis Example 3) Polymer C ′: Synthesis Example of Urethane Acrylate at Both Ends of Acrylyl Group 2-hydroxyethyl acrylate is reacted with a 38,000 molecular weight urethane prepolymer synthesized using polypropylene glycol and isophorone diisocyanate As a result, a liquid polymer C ′ was obtained at room temperature.

(Examples 1 to 11, Comparative Examples 1 to 4)
Each compounding substance was added at the blending ratio shown in Table 1, mixed and stirred to prepare a curable composition.

In Table 1, the unit of the amount of each compounding substance is “parts by weight”. In Table 1, polymer A to polymer H and polymer A ′ to polymer C ′ are the polymers obtained in Synthesis Examples 1 to 8 and Comparative Synthesis Examples 1 to 3, respectively. Is as follows. Monomer B is a monomer obtained in Synthesis Example 9 above. Further, in Table 1, “Acrylic group structure” in the examples represents the structure of the portion bonded to the linking group of the general formula (1), and the “linking group” in the examples represents the “acrylic group” in the general formula (1). In the “group structure”, the first bonded group or X in the general formula (1) is shown.
(C: Monomer A)
2-Hydroxy-3-phenoxypropyl acrylate (Product name “Epoxy ester M-600A”, Kyoeisha Chemical Co., Ltd.)
(B1: Photoinitiator)
2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide (Product name: IRGACURE TPO, manufactured by BASF)
(B1: Photoinitiator)
2-Hydroxy-2-methyl-1-phenyl-propan-1-one (Product name: IRGACURE 1173, manufactured by BASF)
(B1: Photoinitiator)
2-Hydroxy-2-methyl-1-phenyl-propan-1-one (Product name: Darocur 1173, manufactured by BASF)
(B2: thermal initiator)
Di-tert-butyl peroxide (Product name: PERBUTYL D, manufactured by NOF Corporation)

(Surface Curability Test-Photoinitiator)
The photocurable compositions according to Examples 1 to 5, Examples 7 to 11 and Comparative Examples 1 to 3 were used in the air so that the thickness was 200 μm using a glass rod as the adherend (PET film). Applied. Next, the photocurable composition on the adherend was directly irradiated with ultraviolet rays (UV) [irradiation conditions: UV-LED lamp (wavelength 365 nm, illuminance: 1000 mW / cm ² ), integrated light amount: 3000 mJ / cm ^2]. ]. Immediately after UV irradiation, surface curability was tested by finger touch in an environment of 23 ° C. and 50% RH in a dark room. The case where the uncured material did not adhere to the finger or the liquid material adhered but was faint was evaluated as “◯”, and the case where the liquid material adhered to the finger surface was evaluated as “x”.

(Hardness test-photoinitiator)
The hardness test was performed according to JIS K 7312 (1996). First, each of the photocurable compositions according to Examples 1 to 5, Examples 7 to 11, and Comparative Examples 1 to 3 was put in a cap having a height of 6 mm and irradiated with ultraviolet rays (UV) [Irradiation condition: UV LED lamp (wavelength 365 nm, illuminance: 1000 mW / cm ² ), integrated light quantity: 6000 mJ / cm ² ]. Then, two cured products of the photocurable compositions obtained for each of the photocurable compositions according to Examples 1 to 5, Examples 7 to 11, and Comparative Examples 1 to 3 were stacked and placed in an atmosphere at 23 ° C. , Measurement was performed 30 seconds after the pressing surface of the type A durometer was brought into close contact.

(Surface hardening test-thermal initiator)
The thermosetting composition according to Example 6 and Comparative Example 4 was applied to an adherend (aluminum plate) using a glass rod so that the thickness was 200 μm. Next, the thermosetting composition in the adherend was left to stand in a dryer at 180 ° C. for 10 minutes. Immediately after removal from the dryer, the surface curability was tested by finger touch in an environment of 23 ° C. and 50% RH. The case where the uncured material did not adhere to the finger or the liquid material adhered but was faint was evaluated as “◯”, and the case where the liquid material adhered to the finger surface was evaluated as “x”.

(Hardness test-thermal initiator)
The hardness test of the cured product of the thermosetting composition according to Example 6 and Comparative Example 4 was performed according to JIS K 7312 (1996). First, each of the thermosetting compositions according to Example 6 and Comparative Example 4 was put in a metal cap having a height of 6 mm, and left in an atmosphere at 180 ° C. for 10 minutes. Then, two cured products of the thermosetting composition obtained for each of the thermosetting compositions according to Example 6 and Comparative Example 4 were stacked, and in close contact with the pressure surface of the type A durometer in a 23 ° C. atmosphere. It was measured 30 seconds after the test.

As can be seen by referring to Table 1, in the examples, it was shown that the surface curability was good. Moreover, it was shown that the hardened | cured material of the curable composition which concerns on an Example can be adjusted to the hardness of 5 to 70 in a type A durometer by selecting main chain frame | skeleton etc.

From the above, it was shown that in the curable compositions according to the examples, inhibition of polymerization by oxygen was suppressed, excellent curability was exhibited, and physical properties such as hardness of the cured product could be freely adjusted.

The embodiments and examples of the present invention have been described above. However, the embodiments and examples described above do not limit the invention according to the claims. In addition, all the combinations of features described in the embodiments and examples are not necessarily essential to the means for solving the problems of the invention, and various combinations are possible without departing from the technical idea of the present invention. It should be noted that variations are possible.

Claims (13)

1. (A) an organic polymer having a group represented by the following general formula (1);
   A curable composition comprising (B1) a photoinitiator, (B2) a thermal initiator, and (B3) at least one initiator selected from the group consisting of a redox initiator.
   

   

   (In the general formula (1), R ¹ represents —H or —CH ₃ , X represents a linking group, and the linking group is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a polar linking group [ (Thio) ether linking group, —O—CO— linking group, —O—CO—NH— linking group, —NR ² linking group (where R ² is a hydrogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group) An aryl group, a heterocyclic structure-containing group, or a group having a plurality of rings.)], Or a direct bond.
2. The curable composition according to claim 1, further comprising (C) a monofunctional (meth) acrylic monomer.
3. Wherein (C) a monofunctional (meth) acrylic monomer is 3- (meth) acryloxy containing a 2-hydroxypropyl group and a polar group-containing (meth) _acrylates, having a -C _{p H} 2p OH group (meth) acrylate 3. The curable composition according to claim 2, comprising at least one monofunctional (meth) acrylic monomer selected from the group consisting of (wherein p is an integer of 2 to 6) and an alicyclic (meth) acrylate. object.
4. (A) The main chain skeleton of the organic polymer having the group represented by the general formula (1) is a polyoxyalkylene polymer, a (meth) acrylate polymer, a polyester polymer, or a polycarbonate polymer. And at least one organic polymer selected from the group consisting of a graft polymer, a hydrocarbon polymer, a polysulfide polymer, a polyamide polymer, and a diallyl phthalate polymer. The curable composition according to item 1.
5. The curable composition according to any one of claims 1 to 3, wherein the main chain skeleton of the organic polymer (A) having a group represented by the general formula (1) includes a polyoxyalkylene polymer. .
6. The curing according to any one of claims 1 to 3, wherein the main chain skeleton of the organic polymer (A) having a group represented by the general formula (1) includes a (meth) acrylate polymer. Sex composition.
7. The (meth) acrylic acid ester-based polymer is selected from the group consisting of a telechelic type organic polymer, a molecular terminal and functional group copolymer type organic polymer, and a terminal functional group type organic polymer. The curable composition according to claim 6, which is one organic polymer.
8. The curing according to claim 7, wherein the molecular terminal and functional group copolymer type organic polymer or the terminal functional group type organic polymer is a polymer obtained by polymerizing a polymerizable monomer in the presence of a metallocene catalyst. Sex composition.
9. The curable composition according to any one of claims 1 to 3, wherein the main chain skeleton of the organic polymer having the group represented by the general formula (1) includes a polyester polymer.
10. The curable composition according to any one of claims 1 to 3, wherein the main chain skeleton of the organic polymer having a group represented by the general formula (1) includes a polycarbonate polymer.
11. A cured product of the curable composition according to any one of claims 1 to 10.
12. A product having a cured product of the curable composition according to any one of claims 1 to 10 as a constituent element.
13. (A) obtained by reacting a polymer having a predetermined functional group with a functional group having reactivity with the predetermined functional group and a compound having a (meth) acrylate group, represented by the following general formula (1) An organic polymer having a group
    Production of a curable composition obtained by mixing (B1) a photoinitiator, (B2) a thermal initiator, and (B3) at least one initiator selected from the group consisting of a redox initiator to obtain a curable composition. Method.
    

    

    (In the general formula (1), R ¹ represents —H or —CH ₃ , X represents a linking group, and the linking group is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a polar linking group [ (Thio) ether linking group, —O—CO— linking group, —O—CO—NH— linking group, —NR ² linking group (where R ² is a hydrogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group) An aryl group, a heterocyclic structure-containing group, or a group having a plurality of rings.)], Or a direct bond.