JP6683133B2 - Photocurable composition - Google Patents

Description

  The present invention relates to a dual cure type photocurable composition utilizing moisture curing and active energy ray (light) curing. In particular, the present invention relates to a dual cure type photocurable composition which is excellent in temporary fixing property of an adherend immediately after light irradiation and can be cured in a short time.

  An organic polymer having a silicon-bonded group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of being crosslinked by forming a siloxane bond (hereinafter, also referred to as “crosslinkable silicon group”) can be coated or It has the property that it can be made into a liquid that is easy to fill, and that even at room temperature, it can be crosslinked by the formation of siloxane bonds that accompany the hydrolysis reaction of the crosslinkable silicon groups due to the action of moisture in the air, etc., resulting in a cured product. . For this reason, this polymer is widely used for applications such as sealing materials, adhesives and paints. Examples of the polymer having a crosslinkable silicon group include a polyoxyalkylene polymer and a (meth) acrylic acid ester polymer.

  Patent Document 1 discloses an adhesive composition containing a polymer having a hydrolyzable silyl group (corresponding to a crosslinkable silicon group) and a compound having a photopolymerizable polymerizable group. The polymer having a hydrolyzable silyl group is a polymer that is cross-linked and cured by moisture in the air, etc., and the compound having a photopolymerizable polymerizable group is a compound that becomes high in molecular weight by irradiation with light. This adhesive composition is a liquid that can be applied before irradiation with light, and upon irradiation with light, the compound having a photopolymerizable polymerizable group becomes a polymer, and the adherend can be temporarily fixed and fixed. The adherend can be fixed without using a jig. If left as it is, the polymer having a hydrolyzable silyl group contained in the adhesive composition is cured and finally an adhesive having high strength can be obtained.

  Such a curable composition in which a compound having a different curing mechanism is used in combination is called a dual cure type of moisture curing and photocuring in the case of Patent Document 1, and is temporary even without a jig for temporary fixing. It is used for fixing that can be fixed.

  A polymer having a crosslinkable silicon group is cured by moisture by the action of a curing catalyst, but when this polymer is used as an adhesive and thinly applied to an adherend (for example, 500 μm or less), a catalyst having a large catalytic action is used. Then, the moisture instantly penetrates to the inside, and when it is applied, the curing progresses and the bonding work becomes impossible. Further, when a catalyst having a small catalytic action is used, it becomes difficult for the curing to proceed, and complete curing takes time. Thus, when the adhesive is applied thinly, it is difficult to select an appropriate curing catalyst for the polymer having a crosslinkable silicon group.

  Patent Document 2 discloses an adhesive composition which is a dual cure type and uses a photo-acid generator as a curing catalyst for a polymer having a crosslinkable silicon group. In this composition, the generated acid acts as a curing catalyst. In the adhesive composition disclosed in Patent Document 1, curing of the polymer having a crosslinkable silicon group starts at the time of application to the adherend. On the other hand, in the adhesive composition of Patent Document 2, an acid, which is a curing catalyst for a polymer having a crosslinkable silicon group, is generated by light irradiation, and thus curing of the polymer having a crosslinkable silicon group proceeds until light irradiation. do not do. Therefore, according to the adhesive composition described in Patent Document 2, after irradiation with ultraviolet rays, B-stage can be rapidly performed, and problems such as slumping can be avoided.

  However, in the adhesive composition described in Patent Document 2, since the photo-acid generator is used, for example, when amines, alkaline substances and the like are mixed, the active acid catalyst generated from the photo-acid generator reacts. , Cationic photopolymerization is markedly inhibited. This tends to occur not only when a basic adhesion-imparting agent, a filler or the like is mixed in the composition, but also when the adherend contains a basic substance. Therefore, as described in the examples of Patent Document 2, the adhesive composition described in Patent Document 2 does not exhibit sufficient adhesive force immediately after UV irradiation and has poor adhesiveness, and the adherend is also adhered. Limited. In addition, it has a problem of rusting, and cannot be applied to metal adhesion.

JP 2001-139893 A Japanese Patent Publication No. 2009-530441

  Therefore, an object of the present invention is a dual cure type photocurable composition utilizing moisture curing and photocuring, in which curing does not proceed before irradiation of light and sufficient working time can be taken. A dual cure type that produces a cured product with excellent temporary fixability immediately after irradiation, ensures a proper bonding time after light irradiation, and completely cures relatively quickly and does not generate corrosive acid It is to provide a photocurable composition.

  In order to achieve the above-mentioned object, the present invention provides (A) a crosslinkable silicon group-containing organic polymer, (B) a photobase generator, (C1) a silicon compound having a Si—F bond, and (C2) a three-component compound. One or more fluorine-based compounds selected from the group consisting of boron fluoride, a complex of boron trifluoride, a fluorinating agent, and an alkali metal salt of a polyvalent fluoro compound, and (D) one in one molecule. A photocurable composition containing a polyfunctional compound having more than (meth) acryloyl groups is provided.

  Further, the photocurable composition comprises (E) a crosslinkable silicon group-containing compound which, upon irradiation with light, produces at least one amino group selected from the group consisting of primary amino groups and secondary amino groups. It is preferable to further include.

  The photocurable composition preferably further contains (F) a monofunctional compound having a photopolymerizable unsaturated group.

  Further, it is preferable that the photocurable composition further contains (G) a tackifying resin.

  In the above photocurable composition, the crosslinkable silicon group-containing organic polymer (A) is composed of a crosslinkable silicon group-containing polyoxyalkylene polymer and a crosslinkable silicon group-containing (meth) acrylic polymer. It is preferable that it is one or more selected from the group.

  Further, in the above photocurable composition, the photobase generator (B) is preferably a photolatent tertiary amine. Here, a substance that generates an amine compound by the action of active energy rays is referred to as a photolatent amine compound. In addition, a substance that generates an amine compound having a primary amino group by the action of active energy rays is a photolatent primary amine, and a substance that generates an amine compound having a secondary amino group is a photolatent primary compound. A substance that generates an amine compound having a secondary amine and a tertiary amino group is referred to as a photolatent tertiary amine, respectively.

  Further, in the photocurable composition, the organic polymer (A) having a crosslinkable silicon group is a polymer (a-1) having a crosslinkable silicon group and a photoradical polymerizable vinyl group in the molecule ( However, it is preferably selected from the group consisting of organic polymers having a crosslinkable silicon group other than those having a Si—F bond) and (a-2) and (a-1).

  Further, in order to achieve the above object, the present invention provides a cured product obtained by irradiating the above photocurable composition with light.

  Moreover, in order to achieve the said objective, this invention provides the product manufactured using the said photocurable composition. Furthermore, in order to achieve the above object, the present invention provides a product using the above-mentioned photocurable composition as an adhesive. Further, in order to achieve the above object, the present invention provides an electronic device product using the photocurable composition.

  Further, in order to achieve the above object, the present invention is a method for reworking electronic equipment, comprising: (a) an in-situ moldable liquid gasket for electronic equipment; (A) a crosslinkable silicon group-containing organic polymer; ) In-situ moldable liquid gasket containing a photobase generator, (C1) a silicon compound having a Si-F bond, and (D) a polyfunctional compound having more than one (meth) acryloyl group in one molecule. And (b) applying a liquid gasket in an uncured state to one of the housing members of the electronic device to be sealed, irradiating with active energy rays, and sandwiching the other housing member. (C) A method of reworking an electronic device, comprising the steps of removing a housing member of the electronic device that requires reworking after curing and replacing internal components.

  According to the present invention, a dual cure type photo-curable composition utilizing moisture curing and photo-curing, in which curing does not proceed before light irradiation and sufficient working time can be taken, Immediately after that, a cured product with excellent temporary fixability is generated, and after the light irradiation, while maintaining an appropriate bonding time, it is completely cured relatively quickly and does not generate corrosive acid. A photocurable composition can be provided.

  Embodiments of the present invention will be described below, but it goes without saying that these are shown as examples and various modifications can be made without departing from the technical idea of the present invention.

  The photocurable composition according to the present embodiment includes (A) a crosslinkable silicon group-containing organic polymer, (B) a photobase generator, and (C1) a silicon compound having a Si—F bond, and / or (C2) one or more fluorine-based compounds selected from the group consisting of boron trifluoride, a complex of boron trifluoride, a fluorinating agent and an alkali metal salt of a polyvalent fluoro compound, and (D) in one molecule And a polyfunctional compound having more than one (meth) acryloyl group. In the description of the present embodiment, the photocurable composition according to the present embodiment may be referred to as the “compound according to the present embodiment”.

[(A) Crosslinkable Silicon Group-Containing Organic Polymer]
The (A) crosslinkable silicon group-containing organic polymer is not particularly limited as long as it is an organic polymer having a crosslinkable silicon group. In the present embodiment, the main chain is an organic polymer that is not polysiloxane, and organic polymers having various main chain skeletons other than polysiloxane are easily available, and are factors of contact failure in the field of electrical applications. It is preferable in that it does not contain or generate a low molecular cyclic siloxane. The crosslinkable silicon group-containing organic polymer (A) may have a photoradical polymerizable vinyl group together with the crosslinkable silicon group. (A) The crosslinkable silicon group-containing organic polymer further has a photoradical-polymerizable vinyl group in the molecule, whereby the initial tackiness and / or flexibility of the photocurable composition according to the present embodiment can be improved. It can be more easily held, and the heat resistance and the like due to post-curing can be further improved. In the present embodiment, a polymer having a crosslinkable silicon group and a photoradical polymerizable vinyl group in the molecule (excluding those having a Si-F bond) is referred to as a component (a-1), and further, An organic polymer having a crosslinkable silicon group other than (a-1) is referred to as a component (a-2). As the crosslinkable silicon group-containing organic polymer (A), the component (a-1) and / or the component (a-2) can be used.

  The main chain skeleton of the crosslinkable silicon group-containing organic polymer (A) is specifically a polyoxyalkylene polymer such as polyoxypropylene, polyoxytetramethylene, or polyoxyethylene-polyoxypropylene copolymer. A hydrocarbon-based polymer such as an ethylene-propylene-based copolymer, polyisobutylene, polyisoprene, polybutadiene, a hydrogenated polyolefin-based polymer obtained by hydrogenating these polyolefin-based polymers; a dibasic base such as adipic acid Polyester polymer obtained by condensation of acid and glycol or ring-opening polymerization of lactones; (meth) acrylic acid ester obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate -Based polymers; (meth) acrylic acid ester-based monomers, vinyl acetate, acrylo Vinyl-based polymers obtained by radical polymerization of monomers such as tolyl and styrene; graft polymers obtained by polymerizing vinyl monomers in organic polymers; polysulfide-based polymers; polyamide-based polymers; polycarbonate-based polymers A diallyl phthalate polymer and the like can be mentioned. These skeletons may be contained alone in the crosslinkable silicon group-containing organic polymer (A), or two or more kinds thereof may be contained in a block or random manner.

  Further, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester polymers have relatively low glass transition temperatures, and are obtained. It is preferable because the cured product has excellent cold resistance. Further, the polyoxyalkylene polymer and the (meth) acrylic acid ester polymer are particularly preferable because they have high moisture permeability and excellent deep-part curability when formed into a one-pack type composition.

  The crosslinkable silicon group of the (A) crosslinkable silicon group-containing organic polymer is a group that has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond. As the crosslinkable silicon group, for example, a group represented by the general formula (1) is suitable.

In formula (1), R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Group, an aralkyl group having a carbon number of 7 to 20, a triorganosiloxy group represented by R ¹ ₃ SiO— (R ¹ is the same as the above), or a —CH ₂ OR ¹ group (R ¹ is the same as the above). Is. Further, in R ¹ , at least one hydrogen atom on the carbon atoms at the 1st to 3rd positions is halogen, —OR ⁴¹ , —NR ⁴² R ⁴³ , —N = R ⁴⁴ , —SR ⁴⁵ (R ⁴¹ , R ⁴² , R ⁴³ , and R ⁴⁵ are each a hydrogen atom, or a hydrocarbon group having a substituent having 1 to 20 carbon atoms or having no substituent, and R ⁴⁴ is a divalent substituent having 1 to 20 carbon atoms. A hydrocarbon group having a group or having no substituent), a perfluoroalkyl group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a cyano group. Of these, R ¹ is preferably a methyl group. When two or more R ^1's are present, the plurality of R ^1's may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more X are present, a plurality of X may be the same or different. a is an integer of 0, 1, 2 or 3. In consideration of curability, in order to obtain a curable composition having a sufficient curing rate, a in the formula (1) is preferably 2 or more, and more preferably 3.

  The hydrolyzable group and the hydroxyl group 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 number of silicon atoms forming the crosslinkable silicon group may be one, or may be two or more, but in the case of silicon atoms connected by a siloxane bond or the like, the number may be about 20.

  The hydrolyzable group represented by X is not particularly limited as long as it is other than F atom. For example, an alkoxy group, an acyloxy group, an amino group, an amido group, an aminooxy group, an alkenyloxy group and the like can be mentioned. Among these, an alkoxy group is preferable from the viewpoint of mild hydrolyzability and easy handling. Among the alkoxy groups, those having a smaller number of carbon atoms have higher reactivity, and the reactivity becomes lower as the number of carbon atoms increases, in the order of methoxy group> ethoxy group> propoxy group. A methoxy group or an ethoxy group is usually used, though it can be selected according to the purpose or application.

Specific examples of the crosslinkable silicon group include a trialkoxysilyl group such as a trimethoxysilyl group and a triethoxysilyl group [-Si (OR) ₃ ], a dialkoxy group such as a methyldimethoxysilyl group and a methyldiethoxysilyl group. Examples thereof include a silyl group [-SiR ¹ (OR) ₂ ], a trialkoxysilyl group [—Si (OR) ₃ ] is preferable in terms of high reactivity, and a trimethoxysilyl group is more preferable. Here, R is an alkyl group such as a methyl group or an ethyl group.

  The crosslinkable silicon group may be used alone or in combination of two or more. The crosslinkable silicon group may be present in the main chain, the side chain or both. Further, a plurality of crosslinkable silicon groups represented by the general formula (1) may be linked to each other. In this case, the number of silicon atoms forming the crosslinkable silicon group is 1 or more, but in the case of silicon atoms connected by a siloxane bond or the like, it is preferable that the number of silicon atoms is 20 or less. Examples of the photoradical-polymerizable vinyl group include groups containing a (meth) acryloyl group such as a (meth) acryloyloxy group.

  The organic polymer having a crosslinkable silicon group, and the organic polymer having a crosslinkable silicon group and a photoradical polymerizable vinyl group, respectively, may have a linear or branched, the number average molecular weight is The polystyrene conversion in GPC is about 500 to 100,000, more preferably 1,000 to 50,000, and particularly preferably 3,000 to 30,000. When the number average molecular weight is less than 500, it tends to be inconvenient in terms of elongation properties of the cured product, and when it exceeds 100,000, it tends to be inconvenient in terms of workability due to high viscosity.

  In order to obtain a rubber-like cured product having high strength, high elongation, and low elastic modulus, a crosslinkable silicon group contained in an organic polymer having a crosslinkable silicon group, a crosslinkable silicon group and a photoradical polymerizable The crosslinkable silicon groups and photoradical-polymerizable vinyl groups contained in the organic polymer having a vinyl group are on average 0.8 or more, preferably 1.0 or more in one molecule of the polymer, and Preferably, 1.1 to 5 are present. When the number of crosslinkable silicon groups contained in the molecule and the photoradical-polymerizable vinyl groups are less than 0.8 on average, the curability becomes insufficient and it is difficult to exhibit good rubber elasticity behavior. Become. The crosslinkable silicon group and the photoradical-polymerizable vinyl group may be at the end of the main chain of the organic polymer molecular chain or at the end of the side chain, or at both ends. In particular, when the crosslinkable silicon group is only at the end of the main chain of the molecular chain, the effective network length of the organic polymer component contained in the finally formed cured product becomes long, so that high strength and high elongation are obtained. It becomes easy to obtain a rubber-like cured product having a low elastic modulus.

The polyoxyalkylene polymer is essentially a polymer having a repeating unit represented by the general formula (2).
-R ² -O- ··· ⁽²⁾
In the general formula (2), R ² 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 of is more preferable.

Specific examples of the repeating unit represented by the general formula (2) include:
_{-CH 2 O -, - CH 2} CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H 5) O -, - CH 2 C (CH 3) 2 O-, _{-CH 2 CH 2 CH 2 CH 2} O- and the like. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one kind of repeating unit or may be composed of two or more kinds of repeating units.

  Examples of the method for synthesizing the polyoxyalkylene polymer include, but are not particularly limited to, a polymerization method using an alkali catalyst such as KOH, and a polymerization method using a double metal cyanide complex catalyst. According to the polymerization method using a double metal cyanide complex catalyst, a polyoxyalkylene polymer having a high molecular weight of 6,000 or more and Mw / Mn of 1.6 or less and a narrow molecular weight distribution 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; obtained by reacting aliphatic polyisocyanates such as isophorone diisocyanate with polyoxyalkylene polymers having a hydroxyl group. The ingredients can be mentioned.

  A polyoxyalkylene polymer having a functional group such as an unsaturated group, a hydroxyl group, an epoxy group, or an isocyanate group in a molecule, a functional group reactive with this functional group, and a crosslinkable silicon group, and / or Alternatively, a crosslinkable silicon group and / or a photoradical-polymerizable vinyl group can be introduced into a polyoxyalkylene polymer by reacting a compound having a photoradical-polymerizable vinyl group (hereinafter, referred to as polymer reaction method. ).

  As a specific example of the polymer reaction method, a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group is allowed to act on an unsaturated group-containing polyoxyalkylene polymer to hydrosilylate or mercapto, thereby forming a crosslinkable silicon. A method for obtaining a polyoxyalkylene polymer having a group can be mentioned. The unsaturated group-containing polyoxyalkylene polymer is an organic polymer having a functional group such as a hydroxyl group, and an organic compound having an active group and an unsaturated group reactive with this functional group is reacted to form an unsaturated group. It is possible to obtain a polyoxyalkylene polymer containing

  As another specific example of the polymer reaction method, a polyoxyalkylene polymer having a hydroxyl group at the terminal is reacted with an isocyanate group, and a compound having a crosslinkable silicon group and / or a photoradical polymerizable vinyl group. And a method of reacting a polyoxyalkylene polymer having an isocyanate group at the terminal with a compound having an active hydrogen group such as a hydroxyl group or an amino group, and a crosslinkable silicon group and / or a photoradical polymerizable vinyl group. Can be mentioned. When an isocyanate compound is used, a polyoxyalkylene polymer having a crosslinkable silicon group and / or a photoradical polymerizable vinyl group can be easily obtained.

  The polyoxyalkylene polymer having a crosslinkable silicon group and / or a photoradically polymerizable vinyl group may be used alone or in combination of two or more kinds.

  The saturated hydrocarbon polymer is a polymer which does not substantially contain other carbon-carbon unsaturated bond except an aromatic ring. The polymer forming the skeleton is (1) polymerized with an olefinic compound having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene, and isobutylene as a main monomer, or (2) diene such as butadiene and 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. Isobutylene-based polymers and hydrogenated polybutadiene-based polymers are preferable because it is easy to introduce a functional group at the terminal, it is easy to control the molecular weight, and the number of terminal functional groups can be increased, and the isobutylene-based polymer is particularly preferable. preferable. When the main chain skeleton is a saturated hydrocarbon polymer, it has excellent heat resistance, weather resistance, durability and moisture barrier properties.

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

  As a method for synthesizing the saturated hydrocarbon polymer, various polymerization methods can be mentioned. In particular, various living polymerizations have been developed. In the case of saturated hydrocarbon-based polymers, especially isobutylene-based polymers, the inifer polymerization found by Kennedy et al. (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1997, 15: 2843). Easy to manufacture. According to this polymerization method, a polymer having a molecular weight of about 500 to 100,000 can be polymerized with a molecular weight distribution of 1.5 or less, and various functional groups can be introduced at the molecular ends.

  Examples of the method for producing a saturated hydrocarbon polymer having a crosslinkable silicon group and / or a photoradical-polymerizable vinyl group include, for example, a combination of an organic halogen compound that generates a stable carbon cation and a Friedel-Crafts acid catalyst. There may be mentioned a cationic polymerization method in which is used as a copolymerization initiator. An example is the inifer method disclosed in Japanese Patent Publication No. 4-69659.

  The saturated hydrocarbon polymer having a crosslinkable silicon group and / or a photoradical-polymerizable vinyl group may be used alone or in combination of two or more kinds.

  Various monomers can be used as the (meth) acrylic acid ester-based monomer that constitutes the main chain of the (meth) acrylic acid ester-based polymer. For example, (meth) acrylic acid-based monomers such as acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid alkyl ester-based monomers such as stearyl acid acid; alicyclic (meth) acrylic acid ester-based monomers; aromatic (meth) acrylic acid ester-based monomers; (meth) acrylic acid 2-methoxyethyl and the like (meth ) Acrylic ester-based monomers; silyl group-containing (meth) acrylic ester-based monomers such as γ- (methacryloyloxypropyl) trimethoxysilane and γ- (methacryloyloxypropyl) dimethoxymethylsilane; (meth) acrylic acid derivatives; Examples include fluorine-containing (meth) acrylic acid ester-based monomers Be done.

  In the (meth) acrylic acid ester-based polymer, the following vinyl-based monomer can be copolymerized with the (meth) acrylic acid ester-based monomer. Examples of vinyl monomers include styrene, maleic anhydride, vinyl acetate and the like. Further, as the monomer unit (hereinafter, also referred to as other monomer unit), acrylic acid or glycidyl acrylate may be contained in addition to these.

  These may be used alone or a plurality of them may be copolymerized. From the physical properties of the product and the like, a polymer composed of a (meth) acrylic acid type monomer is preferable. Further, a (meth) acrylic acid ester-based polymer in which one kind or two or more kinds of (meth) acrylic acid alkyl ester monomers are used and other (meth) acrylic acid monomers are optionally used in combination is more preferable. Furthermore, the number of silicon groups in the (meth) acrylic acid ester polymer (A) can be controlled by using a silyl group-containing (meth) acrylic acid ester monomer in combination. A methacrylic acid ester-based polymer composed of a methacrylic acid ester monomer is particularly preferable because it has good adhesiveness. Further, in the case of lowering the viscosity, imparting flexibility and imparting tackiness, it is preferable to use an acrylic acid ester monomer in a timely manner. In addition, in this embodiment, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  The method for producing the (meth) acrylic acid ester-based polymer is not particularly limited, and for example, a radical polymerization method using a radical polymerization reaction can be used. Examples of the radical polymerization method include a radical polymerization method in which a predetermined monomer unit is copolymerized using a polymerization initiator (free radical polymerization method), and a reactive silyl group and / or a photoradical at a position controlled such as a terminal. A controlled radical polymerization method capable of introducing a polymerizable vinyl group is mentioned. 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 has a high viscosity. Therefore, in order to obtain a (meth) acrylic acid ester-based polymer having a narrow molecular weight distribution and a low viscosity, and having a high proportion of a (meth) acrylic acid ester-based polymer having a crosslinkable functional group at the molecular chain end, It is preferable to use the 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, and an addition-cleavage transfer reaction (Reversible Addition-Fragmentation chain Transfer; RAFT) polymerization method, A living radical polymerization method such as a radical polymerization method using a transition metal complex (Transition-Metal-Mediated Living Radical Polymerization) is more preferable. Further, a reaction using a thiol compound having a reactive silyl group and a reaction using a thiol compound having a reactive silyl group and a metallocene compound are also suitable.

  The (meth) acrylic acid ester-based polymer having a crosslinkable silicon group and / or a photoradical-polymerizable vinyl group may be used alone or in combination of two or more kinds.

  These organic polymers having a crosslinkable silicon group and / or a photoradical-polymerizable vinyl group may be used alone or in combination of two or more kinds. Specifically, a polyoxyalkylene polymer having a crosslinkable silicon group and / or a photoradical polymerizable vinyl group, a saturated hydrocarbon polymer having a crosslinkable silicon group and / or a photoradical polymerizable vinyl group , And an organic polymer obtained by blending two or more kinds selected from the group consisting of (meth) acrylic acid ester-based polymers having a crosslinkable silicon group and / or a photoradical-polymerizable vinyl group.

As a method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group, various methods can be mentioned. For example, having a crosslinkable silicon group, the molecular chain is substantially represented by the general formula (3):
_{^{-CH 2 -C (R 3) (}} COOR 4) - ··· (3)
(In the formula, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group having 1 to 5 carbon atoms), and a (meth) acrylic acid ester monomer unit represented by the general formula (4):
_{^{-CH 2 -C (R 3) (}} COOR 5) - ··· (4)
(Wherein R ³ is the same as above, R ⁵ represents an alkyl group having 6 or more carbon atoms), and a crosslinkable silicon group is added to the copolymer composed of the (meth) acrylic acid ester monomer unit. And a method for producing by blending a polyoxyalkylene polymer having

R ^{4 in the} general formula (3) has, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, or the like and has 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms, Preferred is an alkyl group having 1 to 2 carbon atoms. The alkyl group of R ⁴ may alone, or may be a mixture of two or more.

R ^{5 in the} general formula (4) is, for example, a 2-ethylhexyl group, a lauryl group, a stearyl group or the like having 6 or more carbon atoms, usually 7 to 30 carbon atoms, preferably 8 to 20 carbon atoms long. Examples include chain alkyl groups. The alkyl group of R ⁵ may be used alone or in combination of two or more, as in the case of R ⁴ .

  The molecular chain of the (meth) acrylic acid ester-based copolymer consists essentially of the monomer units of formula (3) and formula (4). Here, "substantially" means that the total of the monomer units of formula (3) and formula (4) present in the copolymer exceeds 50% by mass. The total of the monomer units of formula (3) and formula (4) is preferably 70% by mass or more. In addition, the abundance ratio of the monomer unit of formula (3) and the monomer unit of formula (4) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40 in terms of mass ratio.

  Having a crosslinkable silicon group used in the method for producing an organic polymer blended with a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group (meth) As the acrylic acid ester-based polymer, for example, a (meth) acrylic acid alkyl ester monomer unit having a crosslinkable silicon group and a molecular chain substantially (1) having an alkyl group having 1 to 8 carbon atoms, And (2) a (meth) acrylic acid ester-based copolymer such as a (meth) acrylic acid ester-based copolymer containing a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having 10 or more carbon atoms. Coalescence can also be used.

  The number average molecular weight of the (meth) acrylic acid ester-based polymer is preferably 600 to 10,000, more preferably 600 to 5,000, and even more preferably 1,000 to 4,500. By setting the number average molecular weight within this range, the compatibility with the polyoxyalkylene polymer having a crosslinkable silicon group is improved. The (meth) acrylic acid ester polymer may be used alone or in combination of two or more kinds. There is no particular limitation on the compounding ratio of the polyoxyalkylene polymer having a crosslinkable silicon group and the (meth) acrylic acid ester polymer having a crosslinkable silicon group, but it is not limited to the (meth) acrylic acid ester polymer. The (meth) acrylic acid ester polymer is preferably in the range of 10 to 60 parts by mass, and more preferably in the range of 20 to 50 parts by mass, based on 100 parts by mass in total of the polyoxyalkylene polymer. And more preferably in the range of 25 to 45 parts by mass. When the amount of the (meth) acrylic acid ester-based polymer is more than 60 parts by mass, the viscosity becomes high and the workability deteriorates, which is not preferable.

  Further, as a method for producing an organic polymer obtained by blending a (meth) acrylic acid ester-based copolymer having a crosslinkable silicon group, in addition to the above, in the presence of an organic polymer having a crosslinkable silicon group, A method of polymerizing a (meth) acrylic acid ester-based monomer can be used.

[(B) Photobase generator]
The photobase generator (B) acts as a curing catalyst for the (A) crosslinkable silicon group-containing organic polymer when irradiated with light. The photobase generator (B) generates a base and / or a radical by the action of active energy rays such as ultraviolet rays, electron rays, X-rays, infrared rays, and visible rays. (1) Salts of organic acids and bases that are decarboxylated and decomposed by irradiation with active energy rays such as ultraviolet rays, visible light, and infrared rays, and (2) amines that are decomposed by intramolecular nucleophilic substitution reaction and rearrangement reaction. A known photobase generator (B) such as a releasing compound or (3) a compound releasing a base by causing a predetermined chemical reaction upon irradiation with energy rays such as ultraviolet rays, visible light and infrared rays can be used. The base generated from the photobase generator (B) has a function of curing the component (A).

  As the base generated from the photobase generator (B), for example, an organic base such as an amine compound is preferable, and examples thereof include primary alkylamines and primary aromatic amines described in WO2015-088021. Secondary alkylamines, amines having a secondary amino group and a tertiary amino group, tertiary alkylamines, tertiary heterocyclic amines, tertiary aromatic amines, amidines, phosphazene derivatives Can be mentioned. Among these, amine compounds having a tertiary amino group are preferable, and amidines and phosphazene derivatives which are strong bases are more preferable. As the amidines, both acyclic amidines and cyclic amidines can be used, and cyclic amidines are more preferable. These bases may be used alone or in combination of two or more.

  Examples of the acyclic amidines include guanidine compounds and biguanide compounds described in WO2015-088021. In addition, among acyclic amidine compounds, for example, when a photobase generator that generates an aryl-substituted guanidine compound or an aryl-substituted biguanide compound described in WO2015-088021 is used as a catalyst for the polymer (A). It is preferable because the curability of the surface tends to be good and the adhesiveness of the obtained cured product tends to be good.

  Examples of the cyclic amidines include cyclic guanidine compounds, imidazoline compounds, imidazole compounds, tetrahydropyrimidine compounds, triazabicycloalkene compounds, and diazabicycloalkene compounds described in WO2015-088021. To be

  Among the cyclic amidines, 1,8-diazabicyclo [5.4.0] undecene is industrially easily available and has a pKa value of the conjugate acid of 12 or more and shows high catalytic activity. -7 (DBU) and 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) are particularly preferable.

  Various photobase generators can be used as the photobase generator (B). A photolatent amine compound that generates an amine compound by the action of active energy rays is preferable. Examples of the photolatent amine compound include photolatent primary amines that generate an amine compound having a primary amino group by the action of active energy rays, and amine compounds having a secondary amino group by the action of active energy rays. Both the photolatent secondary amine generated and the photolatent tertiary amine generating an amine compound having a tertiary amino group by the action of active energy rays can be used. The photolatent tertiary amine is more preferable because the generated base exhibits high catalytic activity.

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

  Examples of the photolatent tertiary amine include, for example, α-aminoketone derivatives, α-ammonium ketone derivatives, benzylamine derivatives, benzylammonium salt derivatives, α-aminoalkene derivatives, and α-ammonium alkene derivatives described in WO2015-088021. , Amine imides, benzyloxycarbonylamine derivatives that generate amidine by light, salts of carboxylic acids with tertiary amines, and the like.

  Examples of the α-aminoketone compound include 5-naphthoylmethyl-1,5-diazabicyclo [4.3.0] nonane and 5- (4′-nitro) phenacyl-1,5-diazabicyclo [4.3.0]. ] Α-Aminoketone compounds that generate amidines such as nonane, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane (Irgacure 907), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone (Irgacure 369), 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone (Irgacure 379) and other tertiary amines composed of one nitrogen atom Examples include α-aminoketone compounds that generate a tertiary amine having a group.

  Examples of the α-ammonium ketone derivative include 1-naphthoylmethyl- (1-azonia-4-azabicyclo [2,2,2] -octane) tetraphenylborate and 5- (4′-nitro) phenacyl- (5 -Azonia-1-azabicyclo [4.3.0] -5-nonene) tetraphenylborate and the like.

  Examples of the benzylamine derivative include 5-benzyl-1,5-diazabicyclo [4.3.0] nonane and 5- (anthracene-9-yl-methyl) -1,5-diazabicyclo [4.3.0]. Examples thereof include benzylamine derivatives such as nonane and 5- (naphth-2-yl-methyl) -1,5-diazabicyclo [4.3.0] nonane.

  Examples of the benzylammonium salt derivative include (9-anthryl) methyl 1-azabicyclo [2.2.2] octanium tetraphenylborate and 5- (9-anthrylmethyl) -1,5-diazabicyclo [4.3. .0] -5-nonenium tetraphenylborate and the like.

  Examples of the α-aminoalkene derivative include 5- (2 ′-(2 ″ -naphthyl) allyl) -1,5-diazabicyclo [4.3.0] nonane.

  Examples of the α-ammonium alkene derivative include 1- (2′-phenylallyl)-(1-azonia-4-azabicyclo [2,2,2] -octane) tetraphenylborate.

  Examples of the benzyloxycarbonylamine derivative that generates amidine by light include benzyloxycarbonylimidazoles, benzyloxycarbonylguanidines, diamine derivatives and the like described in WO2015-088021.

  Examples of the salt of a carboxylic acid and a tertiary amine include an α-ketocarboxylic acid ammonium salt described in WO2015-088021, a carboxylic acid ammonium salt, and the like.

  Among the photobase generators (B), photolatent tertiary amines are preferable from the viewpoint that the generated base exhibits high catalytic activity, and because of high base generation efficiency and good storage stability as a composition, etc. , Benzyl ammonium salt derivatives, benzyl-substituted amine derivatives, α-aminoketone derivatives and α-ammonium ketone derivatives are preferred. In particular, the α-aminoketone derivative and the α-ammonium ketone derivative are more preferable because the generation efficiency of the base is better, and the α-aminoketone derivative is more preferable because of the solubility in the compound. Among the α-aminoketone derivatives, α-aminoketone compounds that generate amidines are preferable due to the basicity of the generated base, and tertiary amines that have a tertiary amine group composed of one nitrogen atom are easily available. Α-Aminoketone compounds that generate a class are mentioned.

  These photobase generators (B) may be used alone or in combination of two or more. The mixing ratio of the photobase generator (B) is not particularly limited, but is preferably 0.01 to 50 parts by mass, and 0.1 to 40 parts by mass with respect to 100 parts by mass of the (A) crosslinkable silicon group-containing organic polymer. A mass part is more preferable, and 0.5-30 mass parts is still more preferable.

[(C1) Silicon Compound Having Si-F Bond]
The silicon compound having a (C1) Si—F bond acts as a curing catalyst for the (A) crosslinkable silicon group-containing organic polymer. (C1) As the silicon compound having a Si-F bond, various compounds including a silicon group having a Si-F bond (hereinafter, may be referred to as fluorosilyl group) can be used, and there is no particular limitation. Both low molecular weight compounds and high molecular weight compounds can be used. An organosilicon compound having a fluorosilyl group is preferable, and an organic polymer having a fluorosilyl group is more preferable because of its high safety. Further, a low molecular weight organosilicon compound having a fluorosilyl group is preferable from the viewpoint that the composition has a low viscosity.

  Specific examples of the (C1) Si-F bond-containing silicon compound include fluorosilanes described in WO2015-088021 represented by formula (5) and WO2015-088021 represented by formula (6). Preferred examples include the compound having a fluorosilyl group described in (hereinafter also referred to as a fluorinated compound), the organic polymer having a fluorosilyl group described in WO2015-088021 (hereinafter also referred to as a fluorinated polymer), and the like. As.

R ⁶ _4-d SiF _d (5)
(In the formula (5), R ⁶ is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ⁷ SiO— (R ⁷ is each independently 1 to 20 carbon atoms. Of the substituted or unsubstituted hydrocarbon group or an organosiloxy group represented by a fluorine atom), d is any one of 1 to 3, and d is preferably 3. R ⁶ And a plurality of R ^7's are present, they may be the same or different.)

^{_{-SiF d R 6 e Z f ···}} (6)
(In the formula (6), R ⁶ and d are respectively the same as those in the formula (5), Z is independently a hydroxyl group or another hydrolyzable group other than fluorine, and e is any of 0 to 2 And f is any of 0 to 2, and d + e + f is 3. When a plurality of R ⁶ , R ⁷ and Z are present, they may be the same or different.

  Examples of the fluorosilanes represented by the formula (5) include fluorosilanes represented by the formula (5). Examples thereof include fluorodimethylphenylsilane, vinyltrifluorosilane, γ-methacryloxypropyltrifluorosilane and octadecyltrifluorosilane.

In the compound having a fluorosilyl group represented by the formula (6), the hydrolyzable group represented by Z is preferably an alkoxy group from the viewpoint of mild hydrolyzability and easy handling, and R ⁶ is a methyl group. preferable.

When the fluorosilyl group represented by the formula (6) is exemplified, a silicon group having no hydrolyzable group other than fluorine and a fluorosilyl group in which R ⁶ is a methyl group are preferable, and a trifluorosilyl group is more preferable.

  The compound having a fluorosilyl group represented by the formula (6) is not particularly limited, and either a monomolecular compound or a polymer compound can be used. For example, inorganic silicon compounds; low molecular weight organosilicon compounds such as vinyldifluoromethoxysilane, vinyltrifluorosilane, phenyldifluoromethoxysilane, and phenyltrifluorosilane; fluorinated poly having a fluorosilyl group represented by the formula (6) at the end. Examples thereof include high molecular compounds such as siloxane, and fluorosilanes represented by the formula (5) and polymers having a fluorosilyl group represented by the formula (6) at the terminal of the main chain or the side chain are preferable.

  As the organic polymer having a fluorosilyl group (hereinafter, also referred to as a fluorinated polymer), various organic polymers having a Si—F bond can be used.

  The fluorinated polymer is a fluorosilyl group and a single polymer having the same main chain skeleton, that is, the number of fluorosilyl groups per molecule, its bonding position, and the number of F contained in the fluorosilyl group, and It may be a single polymer having the same main chain skeleton, or a mixture of a plurality of polymers in which any or all of them are different. Any of these fluorinated polymers can be suitably used as a resin component of a curable composition exhibiting rapid curing property.

  The fluorinated polymer may be linear or branched. The number average molecular weight of the fluorinated polymer is preferably 3,000 to 100,000 in terms of polystyrene in GPC, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30,000. When the number average molecular weight is less than 3,000, it tends to be inconvenient in terms of elongation properties of the cured product, and when it exceeds 100,000, it tends to be inconvenient in terms of workability due to high viscosity.

  The mixing ratio of the silicon compound (C1) having a Si—F bond is not particularly limited, but when a high molecular compound having a number average molecular weight of 3,000 or more such as a fluorinated polymer is used as the component (C1), (A) The amount is preferably 0.01 to 80 parts by mass, more preferably 0.01 to 30 parts by mass, and even more preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of the crosslinkable silicon group-containing organic polymer. A low molecular weight compound having a fluorosilyl group having a number average molecular weight of less than 3,000 as the component (C1) (for example, a fluorosilane group represented by the formula (5) or a low molecular weight organic compound having a fluorosilyl group represented by the formula (6)). When a silicon compound, an inorganic silicon compound having a fluorosilyl group, etc.) is used, 0.01 to 10 parts by mass is preferable, and 0.05 to 10 parts by mass, relative to 100 parts by mass of the (A) crosslinkable silicon group-containing organic polymer. 5 parts by mass is more preferable.

  The mixing ratio of the photobase generator (B) used as a curing catalyst and the silicon compound (C1) having a Si—F bond is such that (B) :( C1) is in a mass ratio of 1: 0.008 to 1: 300. Is preferable, and 1: 0.016 to 1:40 is more preferable.

[(C2) Fluorine Compound]
The (C2) fluorine-based compound is selected, for example, from the group consisting of boron trifluoride, a complex of boron trifluoride, a fluorinating agent, and an alkali metal salt of a polyvalent fluoro compound described in WO2015-088021. One or more fluorine compounds may be mentioned. The fluorine-based compound functions as a compound that accelerates the hydrolytic condensation reaction of the crosslinkable silicon group, and acts as a curing catalyst for the crosslinkable silicon group-containing organic polymer.

  Examples of the boron trifluoride complex include boron trifluoride amine complex, alcohol complex, ether complex, thiol complex, sulfide complex, carboxylic acid complex, and water complex. Among the boron trifluoride complexes, amine complexes having both stability and catalytic activity are particularly preferable. Examples of the amine compound used for the amine complex of boron trifluoride include monoethylamine and the like.

  The mixing ratio of the (C2) fluorine-based compound is not particularly limited, but is preferably 0.001 to 10 parts by mass, and 0.001 to 5 parts by mass, relative to 100 parts by mass of the (A) crosslinkable silicon group-containing organic polymer. A part is more preferable, and 0.001 to 2 parts by mass is further preferable. These fluorine compounds may be used alone or in combination of two or more.

  The photocurable composition may include at least one selected from the group consisting of (C1) Si-F bond-containing silicon compounds and (C2) fluorine-based compounds. In particular, in the photocurable composition according to the present embodiment, in order to improve the effect as a composition for post-curing (that is, to form an adhesive), a crosslinkable silicon group-containing organic polymer is contained and Si-F bond is contained. It is preferable to include a silicon compound having

[(D) Polyfunctional compound]
(D) As a polyfunctional compound having more than one (meth) acryloyl group in one molecule, a compound having more than one (meth) acryloyloxy group in one molecule or more than one in one molecule The compound which has a (meth) acrylamide group is mentioned. From the viewpoint of storage stability, a compound having more than one (meth) acryloyloxy group in one molecule is preferable. Further, from the viewpoint of reactivity, a compound having more than one (meth) acrylamide group in one molecule is preferable.

  In the present embodiment, the (D) polyfunctional compound has more than one (meth) acryloyl group in one molecule, and preferably has 1.5 or more (meth) acryloyl groups in one molecule.

  As the compound having more than one (meth) acryloyloxy group in one molecule, both a monomer (hereinafter also referred to as a monomer) and a polymer can be used. From the viewpoint of viscosity, a monomer having a (meth) acryloyloxy group is preferable. Further, from the viewpoint of curability, a polymer having a (meth) acryloyloxy group is suitable. In this embodiment, the oligomer and the polymer are collectively referred to as a polymer.

  As a monomer having more than one (meth) acryloyloxy group in one molecule, a monomer having two or more (meth) acryloyloxy groups in one molecule is preferable, for example, polyfunctional (meth) acrylates and the like. Is mentioned.

  Examples of polyfunctional acrylates 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, or difunctional (meth) acrylate monomer such as 2,2-bis (4- (meth) acryloxytetraethoxyphenyl) propane, trimethylolpropane tri Trifunctional (meth) acrylate monomers such as (meth) acrylate, tris [(meth) acryloyloxyethyl] isocyanurate, dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, or pentaerythritol ether. Kishitetora (meth) acrylate such as 4 or more functional (meth) acrylate monomers. A bifunctional (meth) acrylate monomer is preferable from the viewpoint of maintaining the flexibility of the photocurable adhesive, and a trifunctional (meth) acrylate monomer and a tetrafunctional or higher (meth) acrylate monomer from the viewpoint of good reactivity. Is preferred.

  The polymer having more than one (meth) acryloyloxy group in one molecule is not particularly limited as long as it is a polymer having an average of more than one (meth) acryloyloxy group in one molecule. A polymer having an average of 1.5 or more (meth) acryloyloxy groups in one molecule is preferable.

  As the polymer having more than one (meth) acryloyloxy group in one molecule, polyether-based urethane (meth) acrylate (for example, "UV-3700B", "UV-6100B" manufactured by Nippon Gosei Co., Ltd.), polyester Urethane (meth) acrylate (for example, "UV-2000B", "UV-3000B", "UV-7000B" manufactured by Nippon Gosei Co., Ltd., "KHP-11", "KHP-17" manufactured by Negami Kogyo Co., Ltd.), non-aromatic Group polycarbonate-based urethane (meth) acrylate (for example, "Art Resin UN-9200A" manufactured by Negami Kogyo Co., Ltd.), acrylic (meth) acrylate (for example, "RC-300", "RC-100C", and "RC manufactured by Kaneka Corporation" -200C "), 1,2-polybutadiene terminated urethane (meth) acrylate (for example," TE manufactured by Nippon Soda Co., Ltd. " 2000 "," TEA-1000 "), hydrogenated product of 1,2-polybutadiene terminated urethane (meth) acrylate (for example," TEAI-1000 "manufactured by Nippon Soda Co., Ltd.), 1,4-polybutadiene terminated urethane (meth) acrylate. (For example, "BAC-45" manufactured by Osaka Organic Chemical Co., Ltd.), polyisoprene-terminated (meth) acrylate, bisphenol A type epoxy (meth) acrylate and the like can be mentioned.

  From the viewpoint of compatibility with the component (A), polyether-based urethane (meth) acrylate, acrylic (meth) acrylate, polyester-based urethane (meth) acrylate and non-aromatic polycarbonate-based urethane (meth) acrylate are preferable, and (A) ) Component is good, and from the viewpoint of ensuring flexibility of the cured product, polyether-based urethane (meth) acrylate and acrylic (meth) acrylate are more preferable, and polyether-based urethane (meth) acrylate is further preferable. .

  As the compound having more than one (meth) acrylamide group in one molecule, a compound having two or more (meth) acrylamide groups in one molecule is preferable, and examples thereof include methylenebisacrylamide, ethylenebisacrylamide and methylenebis. Methacrylamide, oxydimethylene bis acrylamide, ethylene dioxy bis (N-methylene acrylamide) and the like can be mentioned.

  The mixing ratio of the (D) polyfunctional compound is not particularly limited, but is preferably 0.01 to 100 parts by mass, and 0.1 to 100 parts by mass, relative to 100 parts by mass of the (A) crosslinkable silicon group-containing organic polymer. Is more preferable, and 0.2 to 100 parts by mass is further preferable. These (D) polyfunctional compounds may be used alone or in combination of two or more.

[(E) Crosslinkable Silicon Group-Containing Compound that Generates Amino Group by Light]
The photocurable composition according to this embodiment contains (E) a crosslinkable silicon group that generates, when exposed to light, one or more amino groups selected from the group consisting of primary amino groups and secondary amino groups. The compound may further be included. (E) The crosslinkable silicon group-containing compound that produces one or more amino groups selected from the group consisting of primary amino groups and secondary amino groups by light improves the adhesive performance.

  Examples of the crosslinkable silicon group-containing compound that generates one or more amino groups selected from the group consisting of primary amino groups and secondary amino groups by light include a primary amino group and a secondary amino group by light irradiation. Any compound that generates an aminosilane compound having one or more amino groups selected from the group consisting of secondary amino groups and a crosslinkable silicon group can be used. In the present embodiment, the crosslinkable silicon group-containing compound that generates one or more amino groups selected from the group consisting of primary amino groups and secondary amino groups by light is also referred to as a photoaminosilane-generating compound.

  As the aminosilane compound generated by light irradiation, a compound having a crosslinkable silicon group and a substituted or unsubstituted amino group is used. Examples of the substituent of the substituted amino group include an alkyl group, an aralkyl group, an aryl group and the like. Of these, an alkyl group is preferable from the viewpoint of good adhesion. As the crosslinkable silicon group, a silicon-containing group having a hydrolyzable group bonded thereto is preferable. Among these, alkoxy groups such as methoxy group and ethoxy group are preferable because they have mild hydrolyzability and are easy to handle. In the aminosilane compound, the hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, preferably 2 or more, and particularly preferably 3.

The aminosilane compound generated by light irradiation is not particularly limited, and an aminosilane compound having a primary amino group (—NH ₂ ) is preferable from the viewpoint of adhesiveness, γ-aminopropyltrimethoxysilane from the viewpoint of availability, γ-Aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane and γ- (2-aminoethyl) aminopropyltrimethoxysilane are preferable, and γ-aminopropyltrimethoxysilane and γ-aminopropyl are preferable in terms of adhesiveness and curability. Triethoxysilane is more preferred.

  Examples of the photoaminosilane-generating compound include photofunctional silicon compounds, aromatic sulfonamide derivatives, O-acyloxime derivatives, and trans-, which are represented by formulas (7) to (8) and described in WO2015-088021. Examples thereof include O-coumaric acid derivatives.

In formula (7), n is an integer of 1 to 3, Y represents a hydroxyl group or a hydrolyzable group, and an alkoxy group is preferable. When there are a plurality of Y's, they may be the same or different. R ⁸ represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a substituent, a vinyl group, an allyl group, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, an unsubstituted or substituted aryl group Is preferred. When there are a plurality of R ^8's , they may be the same or different. R ⁹ is a hydrogen atom or an organic group, preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a substituent, and more preferably a hydrogen atom. h is an integer of 1 to 5, and j is an integer of 1 to 6. R ¹⁰ is a substituted or unsubstituted hydrocarbon group bonded to a silicon atom and a nitrogen atom at h + j different carbon atoms, and a plurality of substituted or unsubstituted hydrocarbon groups bonded to each other through one or more ether oxygen atoms. It is an h + j-valent group selected from the group consisting of hydrocarbon groups and has a molecular weight of 1,000 or less. R ⁹ and R ¹⁰ may be bonded to each other to form a cyclic structure, or may include a bond of a hetero atom. Z is an oxygen atom or a sulfur atom, and an oxygen atom is preferable. Q represents a photofunctional group.

In formula (8), n, Y, R ⁸ , Z, and Q are the same as in formula (7). R ¹² is a divalent group selected from the group consisting of a substituted or unsubstituted hydrocarbon group and a plurality of substituted or unsubstituted hydrocarbon groups bonded to each other through one or more ether oxygen atoms. . t is an integer of 1 or more, preferably 1 or 2. When t is 2 or more, t groups bonded to R ¹¹ may be the same or different. R ¹¹ is a hydrogen atom or an organic group, preferably a hydrogen atom or a substituted or unsubstituted t-valent hydrocarbon group, and more preferably a hydrogen atom or a substituted or unsubstituted t-valent alkyl group. R ¹¹ and R ¹² may be bonded to each other to form a cyclic structure, or may include a bond of a hetero atom.

  The photofunctional group Q is not particularly limited and may be a known photosensitive group, and examples thereof include a group having a cyclic structure described in WO2015-088021, a oxime residue and these substituted groups. A group having a cyclic structure is preferable.

  Examples of the group having a cyclic structure include an aromatic group described in WO2015-088021, a group having a heterocyclic structure, and these substituted groups, and an aromatic group is preferable. Further, the groups in the photofunctional group may be bonded to each other to form a cyclic structure.

  Examples of the aromatic group include nitro such as o-nitrobenzyl group described in WO2015-088021, m-nitrobenzyl group described in WO2015-088021, and p-nitrobenzyl group described in WO2015-088021. Examples thereof include a benzyl group, a benzyl group described in WO2015-088021, and a benzoyl group and these substituted groups. A nitrobenzyl group is preferable, an o-nitrobenzyl group and a p-nitrobenzyl group are more preferable, and o The -nitrobenzyl group is particularly preferred. Further, the groups in the photofunctional group may be bonded to each other to form a cyclic structure.

  Examples of the group having a heterocyclic structure include a coumarin derivative residue described in WO2015-088021, and an imide group and these substituted groups.

  Examples of the —OQ group in which the photofunctional group Q is an o-nitrobenzyl group include, for example, a (2,6-dinitrobenzyl) oxy group, a (2-nitrobenzyl) oxy group, and a (3,4-dimethoxy-2-nitro) group. And a nitrobenzyloxy group such as a (benzyl) oxy group.

  Examples of the -OQ group in which the photofunctional group Q is a p-nitrobenzyl group include, for example, (2,4-dinitrobenzyl) oxy group, (4-nitrobenzyl) oxy group, [1- (4-nitronaphthalene) methyl group. ] A nitrobenzyloxy group such as an oxy group can be mentioned.

  Examples of the -OQ group in which the photofunctional group Q is a benzyl group include, for example, 3,5-dimethoxybenzyloxy group, [1- (3,5-dimethoxyphenyl) -1-methylethyl] oxy group, 9-anthryl. A benzyloxy group such as a methyloxy group, a 9-fananthrylmethyloxy group, a 1-pyrenylmethyloxy group, a [1- (anthraquinone-2-yl) ethyl] oxy group, a 9-phenylxanthen-9-yloxy group Can be mentioned.

  In formulas (7) and (8), examples of the residue excluding the ZQ group include a 3- (trimethoxysilyl) propylaminocarbonyl group, a 3- (triethoxysilyl) propylaminocarbonyl group, and a 3- (methyl) group. Monoaminocarbonyl groups such as dimethoxysilyl) propylaminocarbonyl group and 3- (methyldiethoxysilyl) propylaminocarbonyl group; N- [3- (trimethoxysilyl) propyl] ethylenediaminocarbonyl group, N, N'-bis Examples include diaminocarbonyl groups such as [3- (trimethoxysilyl) propyl] ethylenediaminocarbonyl group; aminocarbonyl groups such as triaminocarbonyl groups such as N- [3- (trimethoxysilyl) propyl] diethylenetriaminocarbonyl group. .

Among the aminocarbonyl groups, an aminocarbonyl group having an amino group (—NH ₂ ) is preferable from the viewpoint of adhesiveness, and a 3- (trimethoxysilyl) propylaminocarbonyl group or a 3- (triethoxysilyl) propylaminocarbonyl group , 3- (methyldimethoxysilyl) propylaminocarbonyl group and N- [3- (trimethoxysilyl) propyl] ethylenediaminocarbonyl group are more preferable, and 3- (trimethoxysilyl) propylaminocarbonyl group is more preferable in terms of adhesiveness and curability. Most preferred is the 3- (triethoxysilyl) propylaminocarbonyl group.

  The mixing ratio of the photoaminosilane generating compound is not particularly limited, but is preferably 0.01 to 50 parts by mass, and 0.1 to 30 parts by mass with respect to 100 parts by mass of the (A) crosslinkable silicon group-containing organic polymer. More preferably, 0.1 to 20 parts by mass is even more preferable. These photoaminosilane-generating compounds may be used alone or in combination of two or more.

[(F) Monofunctional compound having photopolymerizable unsaturated group]
The photocurable composition according to the present embodiment preferably further contains (F) a monofunctional compound having a photopolymerizable unsaturated group. The monofunctional compound (F) can reduce the viscosity of the photocurable compound. As the monofunctional compound having a photopolymerizable unsaturated group (F), various monofunctional compounds having a photopolymerizable unsaturated group can be used, and there is no particular limitation, but for example, a (meth) acryloyl group And a N-vinyl compound in which a vinyl group is directly bonded to a nitrogen atom.

  The compound having one (meth) acryloyl group in one molecule includes a compound having one (meth) acryloyloxy group in one molecule and a compound having one (meth) acrylamide group in one molecule. Among them, a compound having one (meth) acryloyloxy group in one molecule is preferable from the viewpoint of storage stability. Further, from the viewpoint of reactivity, a compound having one (meth) acrylamide group in one molecule is preferable.

  As the compound having one (meth) acryloyloxy group in one molecule, any of a monomer, an oligomer and a polymer can be used. From the viewpoint of viscosity, a monomer having a (meth) acryloyloxy group is preferable. Further, from the viewpoint of curability, an oligomer having a (meth) acryloyloxy group is suitable.

  The monomer having one (meth) acryloyloxy group in one molecule is not particularly limited as long as it is a compound having one (meth) acryloyloxy group, and examples thereof include monofunctional (meth) acrylates. Is mentioned.

  As the monofunctional (meth) acrylate, as the (meth) acrylate having a hydroxyl group, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hexaethylene glycol mono (meth) acrylate, octapropylene glycol mono (Meth) acrylate 2-hydroxy-3-octyloxypropyl acrylate and the like can be mentioned. Examples of the (meth) acrylate having an alkoxy group include methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate. Examples of aromatic (meth) acrylates include phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, and benzyl (meth) acrylate. Examples of the long-chain hydrocarbon (meth) acrylate having 8 to 20 carbon atoms include 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, and isostearyl (meth) acrylate. From the viewpoint of easy availability, a long-chain hydrocarbon (meth) acrylate having 8 to 18 carbon atoms is preferable. Examples of the alicyclic (meth) acrylate include cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate and the like. Examples of the (meth) acrylate having a heterocyclic group include tetrahydrofurfuryl (meth) acrylate. Moreover, N- (meth) acryloyloxyethyl hexahydrophthalimide etc. are mentioned. Examples of the (meth) acrylate having a crosslinkable silicon group include 3- (trimethoxysilyl) propyl (meth) acrylate. When flexibility is required, monofunctional (meth) acrylates are preferably used.

  As the oligomer having one (meth) acryloyloxy group in one molecule, a polymer having one (meth) acryloyloxy group 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, and a polyether (meth) acrylate polymer. Examples thereof include coalesce and epoxy (meth) acrylate-based polymers.

  Examples of the compound having one (meth) acrylamide group in one molecule include N-methyl (meth) acrylamide and (meth) acrylolylmorpholine.

  Examples of the N-vinyl compound include N-vinylpyrrolidone and N-vinylcaprolactam. In the present embodiment, the N-vinyl compound is preferable from the viewpoint of reactivity and the difficulty of oxygen inhibition.

  The compounding ratio of the (F) monofunctional compound is not particularly limited, but is preferably 0.01 to 100 parts by mass, and 0.1 to 100 parts by mass, relative to 100 parts by mass of the (A) crosslinkable silicon group-containing organic polymer. Parts is more preferable, and 1 to 100 parts by mass is further preferable. These (F) monofunctional compounds may be used alone or in combination of two or more.

[(G) Tackifying resin]
The photocurable composition according to this embodiment preferably further contains (G) a tackifying resin. The tackifying resin (G) is not particularly limited, and examples thereof include commonly used resins. Specific examples include terpene resins, aromatic modified terpene resins, and hydrogenated terpene resins obtained by hydrogenating these, terpenes-phenol resins obtained by copolymerizing terpenes with phenols, phenol resins, modified phenol resins, xylene resins, Xylene-phenol resin, cyclopentadiene resin, cyclopentadiene-phenol resin, coumarone indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, , C5 hydrocarbon resin, C9 hydrocarbon resin, C5, C9 hydrocarbon copolymer resin, C5, C9 hydrocarbon, phenol copolymer resin), hydrogenated petroleum resin and the like. These may be used alone or in combination of two or more.

  Here, when the tackifying resin is used for the adherend having low polarity, it is preferable to use the tackifying resin having low polarity, and when it is used for the adherend having high polarity, the tackifying resin having high polarity is used. Is preferred. When the tackifier resin is used for a wide range of adherends from high-polarity adherends to low-polarity adherends, it is preferable to use a low-polarity tackifying resin and a high-polarity tackifying resin as a mixture. .

  The compounding ratio of the (G) tackifying resin is not particularly limited, but is preferably 0.1 to 100 parts by mass, and 1 to 80 parts by mass with respect to 100 parts by mass of the (A) crosslinkable silicon group-containing organic polymer. More preferable. These tackifying resins may be used alone or in combination of two or more.

[Other additives]
The formulation according to the present embodiment, if necessary, a compound having a (meth) acrylamide group, a compound having an epoxy group, a silane coupling agent, a base-propagating aminosilane, a photoradical polymerization initiator, a photosensitizer, Extenders, diluents, plasticizers, moisture absorbers, silanol condensation catalysts, physical property modifiers that improve tensile properties, reinforcing agents, colorants, flame retardants, anti-sagging agents, antioxidants, anti-aging agents, UV absorption Various additives such as agents, solvents, fragrances, pigments, dyes, conductive powders, heat conductive powders, phosphors, waxes and resin fillers may be further included.

  Examples of the compound having an N-methyl (meth) acrylamide group include N-methyl (meth) acrylamide, N- (meth) acrylolylmorpholine and the like, which have a good balance of curability, physical properties and safety. Therefore, acryloylmorpholine is preferred.

  Examples of the compound having an epoxy group include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, novolac type epoxy resin, aliphatic cyclic epoxy resin, brominated epoxy resin, and rubber. Examples thereof include modified epoxy resin, urethane modified epoxy resin, glycidyl ester compound, epoxidized polybutadiene, and epoxidized SBS (SBS represents a styrene-butadiene-styrene copolymer). When a compound having an epoxy group is further added to the composition according to the present embodiment, the composition according to the present embodiment exhibits high adhesiveness and durability after curing, and particularly to an adherend having an aromatic ring. effective. In addition, when used in combination with a photoaminosilane-generating compound or an aminosilane compound, it is further effective in improving the adhesiveness.

  The composition according to the present embodiment can improve the general adhesiveness to adherends such as metal, plastic, and glass by adding a silane coupling agent.

  Examples of the silane coupling agent include amino group-containing silanes; ketimine type silanes; epoxy group containing silanes; mercapto group containing silanes; vinyl type unsaturated group containing silanes; chlorine atom containing silanes; isocyanate containing silanes. Examples thereof include alkylsilanes, phenyl group-containing silanes, isocyanurate group-containing silanes, and the like, but are not limited thereto. Further, a modified amino group-containing silane obtained by modifying an amino group by reacting an amino group-containing silane with an epoxy group-containing compound containing the above silanes, an isocyanate group-containing compound, and a (meth) acryloyl group-containing compound is used. May be.

  Further, a silane coupling agent may be added for the purpose of crosslinking the tackifying resin and the crosslinkable silicon group-containing organic polymer. When using a tackifying resin containing a phenol or a carboxylic acid, for example, by adding an epoxysilane, it is possible to crosslink the crosslinkable silicon group-containing organic polymer and the tackifying resin, the adhesive force (adhesive strength ), Heat-resistant creep, and changes in the adhesive strength (adhesive strength) due to movement of the tackifying resin during jointing can be suppressed.

  The mixing ratio of the silane coupling agent is not particularly limited, but is preferably 0.2 to 20 parts by mass, and 0.3 to 15 parts by mass with respect to 100 parts by mass of the (A) crosslinkable silicon group-containing organic polymer. More preferably, 0.5 to 10 parts by mass is even more preferable. These silane coupling agents may be used alone or in combination of two or more.

The composition according to this embodiment may further contain a base-propagating aminosilane for the purpose of improving the adhesive performance. Examples of the base-propagating aminosilane include a base-propagating amine compound having a crosslinkable silicon group at an amine residue (a compound that produces an amine compound having a crosslinkable silicon group when decomposed). Examples of such a compound include 9-fluorenylmethyl ester of carbamic acid having a crosslinkable silicon group (C ₁₃ H ₉ CH ₂ OCONR ¹³ R ¹⁴ , where R ¹³ and R ¹⁴ are each a hydrogen atom or a hydrocarbon group). An organic group, at least one of R ¹³ and R ¹⁴ is an organic group such as a hydrocarbon group having a crosslinkable silicon group), a 2-arylsulfonylethyl ester of carbamic acid having a crosslinkable silicon group (ArSO ₂ CH ₂ CH ₂ OCONR ¹³ R ¹⁴ , where Ar is an aromatic group which may have a substituent, R ¹³ and R ¹⁴ are the same as the above), and 3-nitropentane of carbamic acid having a crosslinkable silicon group. 2- yl ester _{(CH 3 CH 2 CH (NO} 2) CH (CH 3) OCONR 13 R 14, ^{wherein, R 13,} R ¹⁴ are as defined above Etc. The.

  Examples of the photoradical polymerization initiator include arylalkyl ketones such as benzoin ether derivatives and acetophenone derivatives, oxime ketones, acylphosphine oxides, S-phenyl thiobenzoates, titanocenes, and high molecular weights thereof. Examples include derivatives.

  The formulation according to this embodiment may further contain a diluent. By adding a diluent, physical properties such as viscosity can be adjusted. Various diluents can be used as the diluent, and there is no particular limitation. For example, saturated hydrocarbon solvents such as normal paraffin and isoparaffin, α-olefin derivatives such as HS dimer (trade name of Toyokuni Oil Co., Ltd.), aromatic hydrocarbon solvents, alcohol solvents such as diacetone alcohol, ester solvents. , Various solvents such as citrate ester solvents such as acetyltriethyl citrate, and ketone solvents.

  Although the flash point of the diluent is not particularly limited, considering the safety of the resulting formulation according to the present embodiment, it is desirable that the flash point of the formulation according to the present embodiment is high, and the combination according to the present embodiment It is preferable that the amount of volatile substances from the product is small. Therefore, the flash point of the diluent is preferably 60 ° C or higher, and more preferably 70 ° C or higher. When two or more diluents are mixed, it is preferable that the mixed diluents have a flash point of 70 ° C or higher. In general, a diluent having a high flash point tends to have a low diluting effect on the composition according to the present embodiment, so that the flash point is preferably 250 ° C. or lower.

  Considering both the safety and the dilution effect of the formulation according to the present embodiment, a saturated hydrocarbon solvent is preferable as the diluent, and normal paraffin and isoparaffin are more preferable. The normal paraffin and isoparaffin preferably have 10 to 16 carbon atoms, and more preferably 14 to 16 carbon atoms from the influence (VOC) on the use environment.

  The mixing ratio of the diluent is not particularly limited, but from the viewpoint of the balance between improvement of coating workability and deterioration of physical properties due to the mixing, the diluent is added in an amount of 0 to 25% relative to the unit weight of the composition. It is preferable that the content is 0.1 to 15%, more preferably 1 to 7%. The diluent may be used alone or in combination of two or more kinds.

  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 system, benzoguanamine resin, phenol resin, acrylic resin and styrene resin can be used.

  The resin filler (resin fine powder) is preferably spherical, which can be easily obtained by suspension polymerization of a monomer (eg, methyl methacrylate) or the like. Further, since the resin filler is preferably contained in the solution composition as a filler, a spherical crosslinked resin filler is preferable.

  As the resin filler, a urethane resin-based filler and an acrylic resin-based filler are preferable, and a urethane resin-based filler is more preferable, in terms of good compatibility with the compound according to the present embodiment.

  The average particle size of the resin filler is preferably 1 to 150 μm, more preferably 5 to 30 μm. In this embodiment, the average particle size is a 50% cumulative particle size measured by a laser diffraction scattering method. If the average particle size is smaller than 1 μm, it may be difficult to disperse the conductive adhesive in the system. If it is larger than 150 μm, the nozzle of the application tends to be clogged.

  The compounding ratio of the resin filler is preferably 0.5 to 200 parts by mass, and more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the component (A). The resin filler may be used alone or in combination of two or more kinds.

  When the composition according to the present embodiment is used for applications requiring light shielding properties, it is preferable that the resin filler contains a black resin filler. By using a black resin filler having an average particle diameter of 1 to 150 μm, good deep-part curability can be obtained even when using a single-wavelength LED lamp or the like, and excellent light-shielding properties and deep-part curability can be obtained. Can be achieved.

  The method for producing the photocurable composition is not particularly limited, and, for example, components (A) to (D) are blended in a predetermined amount, and if necessary, other blended substances are blended, followed by deaeration stirring. Can be manufactured. The order of mixing each component and other compounding substances is not particularly limited and can be appropriately determined.

  The photocurable composition may be a one-pack type or a two-pack type, if necessary, and is particularly preferably used as a one-pack type. The photocurable composition according to the present embodiment is a photocurable composition that is cured by light irradiation, and can be cured at room temperature (for example, 23 ° C.), and is suitably used as a room temperature photocurable composition. However, if necessary, the curing may be appropriately accelerated by heating.

The method for producing a cured product according to this embodiment is a method of forming a cured product by irradiating the photocurable composition according to this embodiment with light. The cured product according to the present embodiment is a cured product obtained by this method.
Further, the method for producing the product according to the present embodiment is a method for producing using the photocurable composition according to the present embodiment. The product according to the present embodiment is a product manufactured by using this method, and can be suitably used for various products such as electronic circuits, electronic components, building materials, and automobiles.

  With respect to the photocurable composition according to the present embodiment, the conditions for irradiating light is not particularly limited, but when irradiating with active energy rays during curing, the active energy rays include ultraviolet rays, visible rays, infrared rays, and the like. In addition to electromagnetic waves such as light rays, X-rays and γ rays, electron rays, proton rays, neutron rays and the like can be used. Curing by UV or electron beam irradiation is preferable, and curing by UV irradiation is more preferable, from the viewpoints of curing speed, availability and cost of irradiation device, ease of handling under sunlight and general illumination. The ultraviolet rays also include g rays (wavelength 436 nm), h rays (wavelength 405 nm), i rays (wavelength 365 nm), and the like. The active energy ray source is not particularly limited, but depending on the properties of the photobase generator used, for example, a high pressure mercury lamp, a low pressure mercury lamp, an electron beam irradiation device, a halogen lamp, a light emitting diode, a semiconductor laser, a metal halide, and the like. , Light emitting diodes are preferred.

The irradiation energy, for example, in the case of UV, preferably 10~20,000mJ / cm ^2, more preferably ^{20~10,000mJ / cm 2, 50~5,000mJ / cm} 2 is more preferable. If it is less than 10 mJ / cm ² , the curability may be insufficient, and if it is more than 20,000 mJ / cm ² , the time and cost may be wasted even if light is irradiated more than necessary, and the base material may be damaged. There is.

  The method for applying the photocurable composition according to the present embodiment to the adherend is not particularly limited, but the application method such as screen printing, stencil printing, roll printing, dispenser application, jet dispenser application, spray application, spin coating, etc. Is preferably used.

  Further, in this embodiment, there is no limitation on the timing of applying the photocurable composition to the adherend and irradiating the light. For example, the photocurable composition can be irradiated with light and then bonded to an adherend to manufacture a product. Further, the photocurable composition can be applied to an adherend and the composition can be cured by irradiating with light to manufacture a product.

  The photocurable composition according to the present embodiment is a fast-curing photocurable composition having excellent workability, and is particularly useful as a viscous / adhesive composition, and is an adhesive, a sealing material, an adhesive material. It can be suitably used as a coating material, potting material, paint, putty material, primer, gasket, and the like. The photocurable composition according to the present embodiment is, for example, a coating agent used for coating a circuit board or the like for the purpose of preventing moisture or insulation, coating a solar power generation panel or a peripheral portion of the panel, and the like; Sealing agents, sealing agents for vehicles, etc., architectural and industrial sealing agents; materials for electrical and electronic parts such as solar cell backside encapsulants; electrical insulating materials such as insulation coatings for wires and cables; stereolithography by stereolithography It can be suitably used for a material for forming a molded article; an adhesive; an adhesive; an elastic adhesive; a contact adhesive; an application requiring rework or repair; an application such as a liquid gasket.

  The liquid gasket can be used, for example, in a Formed In Place Gasket (FIPG) for electronic devices. That is, the photocurable composition according to the present embodiment is liquid before curing. Therefore, the photocurable composition according to the present embodiment is a FIPG for electronic devices, and does not cure even when exposed to air before irradiation with active energy rays, so that sufficient working time can be secured, and active energy rays can be secured. It can be used as a liquid gasket for electronic device products, which cures in a short time while having a sufficient bonding time after irradiation.

  Further, in the housing member joined by using the liquid gasket of the photocurable composition according to the present embodiment, when sandwiching the housing member after irradiation with the active energy ray, the photocurable composition is applied to a portion where sealing of the housing member is not desired. Not only does the liquid gasket formed by using the object not protrude, but also the housing member can be removed with a small force. Moreover, the removal of the housing member is not limited to the initial stage of curing, and the housing member can be removed with a small force even after curing. Then, after removing the housing member, the liquid gasket can be used as it is to rejoin the housing member, and the initial sealing performance such as waterproof performance can be maintained even after the rejoining. However, by further adding a photoaminosilane-generating compound, an aminosilane compound, or the like, it is possible to design so that it can be removed within a certain period of time but cannot be removed after a certain period of time.

  The liquid gasket of the photocurable composition according to the present embodiment is applied to one or both of a plurality of housing members such as a main body or a lid, or a portion to be sealed, and after irradiating with active energy rays, the housing member is It can be used in combination. Since the crosslinkable silicon group-containing organic polymer is cured by moisture in the air after irradiation with active energy rays, curing proceeds if the housing members are left after being combined. Heating may be performed to increase the curing rate.

  Hereinafter, the present invention will be described more specifically with reference to examples. Needless to say, these examples are merely examples and should not be construed as limiting.

1) Measurement of number average molecular weight The number average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions. In the description of the examples, the maximum frequency molecular weight measured by GPC under the following measurement conditions and converted to standard polyethylene is referred to as the number average molecular weight.
-Analyzer: Alliance (manufactured by Waters), 2410 type differential refraction detector (manufactured by Waters), 996 type multi-wavelength detector (manufactured by Waters), Millennium data processor (manufactured by Waters)
・ Column: Plgel GUARD + 5 μm Mixed-C × 3 (50 × 7.5 mm, 300 × 7.5 mm: manufactured by PolymerLab)
・ Flow rate: 1 mL / min ・ Converted polymer: polyethylene ・ Measuring temperature: 40 ° C
・ Solvent for GPC measurement: THF

2) Measurement of NMR and IR The measurement of NMR and IR was performed using the following measuring device.
FT-NMR measuring device: JEM-ECA500 (500 MHz) manufactured by JEOL Ltd.
FT-IR measuring device: FT-IR460Plus manufactured by JASCO Corporation

(Synthesis Example 1) Synthesis of polyoxyalkylene-based polymer A1 having a trimethoxysilyl group at the terminal Polyoxypropylene was reacted with propylene oxide in the presence of zinc hexacyanocobaltate-glyme complex catalyst using ethylene glycol as an initiator. The diol was obtained. A polyoxyalkylene polymer having an allyl group at the terminal of the obtained polyoxypropylene diol was obtained according to the method of Synthesis Example 2 of WO2015-088021. To this polyoxyalkylene polymer having an allyl group at the terminal, trimethoxysilane, which is a silicon hydride compound, is added and reacted with a platinum vinyl siloxane complex isopropanol solution, and polyoxyalkylene having a trimethoxysilyl group at the terminal. A polymer A1 was obtained.

As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A1 having a trimethoxysilyl group at the terminal by GPC, the peak top molecular weight was 25,000 and the molecular weight distribution was 1.3. ^{According to 1} H-NMR measurement, the number of terminal trimethoxysilyl groups was 1.7 per molecule.

(Synthesis Example 2) Synthesis of polyoxyalkylene polymer A2 having a trimethoxysilyl group at the terminal Polyethylene oxide was used as an initiator, and propylene oxide was reacted in the presence of a zinc hexacyanocobaltate-glyme complex catalyst to give polyoxypropylene. The diol was obtained. A polyoxyalkylene polymer having an allyl group at the terminal of the obtained polyoxypropylene diol was obtained according to the method of Synthesis Example 2 of WO2015-088021. To this polyoxyalkylene polymer having an allyl group at the terminal, trimethoxysilane, which is a silicon hydride compound, is added and reacted with a platinum vinyl siloxane complex isopropanol solution, and polyoxyalkylene having a trimethoxysilyl group at the terminal. A polymer A2 was obtained.

As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A2 having a trimethoxysilyl group at the terminal by GPC, the peak top molecular weight was 12,000 and the molecular weight distribution was 1.3. ^{According to 1} H-NMR measurement, the number of terminal trimethoxysilyl groups was 1.7 per molecule.

(Synthesis Example 3) Synthesis of (meth) acrylic polymer A3 having a trimethoxysilyl group Methyl methacrylate 70.00 g, 2-ethylhexyl methacrylate 30.00 g, 3-methacryloxypropyltrimethoxysilane 12.00 g, as a metal catalyst According to the method of Synthesis Example 4 of WO2015-088021 using 0.10 g of titanocene diclide, 8.60 g of 3-mercaptopropyltrimethoxysilane, and 20.00 g of a benzoquinone solution (95% THF solution) as a polymerization terminator. A (meth) acrylic polymer A3 having a trimethoxysilyl group was obtained. The (meth) acrylic polymer A3 had a peak top molecular weight of 4,000 and a molecular weight distribution of 2.4. ^The number of trimethoxysilyl groups contained by ¹ H-NMR measurement was 2.00 per molecule.

(Synthesis Example 4) Synthesis of Fluorinated Polymer C1-1 Using polyoxypropylene diol having a molecular weight of about 2,000 as an initiator, propylene oxide was reacted in the presence of a zinc hexacyanocobaltate-glyme complex catalyst to calculate a hydroxyl value-converted molecular weight. Polyoxypropylene diol having a molecular weight distribution of 1.3 and 14,500 was obtained. A polyoxyalkylene polymer having an allyl group at the terminal of the obtained polyoxypropylene diol was obtained according to the method of Synthesis Example 2 of WO2015-088021. To this polyoxyalkylene polymer having an allyl group at the terminal, methyldimethoxysilane which is a silicon hydride compound is added and reacted with a platinum vinylsiloxane complex isopropanol solution, and polyoxyalkylene having a methyldimethoxysilyl group at the terminal is reacted. A polymer A4 was obtained. The molecular weight of the obtained polyoxyalkylene polymer A4 having a methyldimethoxysilyl group at the terminal was measured by GPC. As a result, the peak top molecular weight was 15,000 and the molecular weight distribution was 1.3. ^{According to 1} H-NMR measurement, the number of terminal methyldimethoxysilyl groups was 1.7 per molecule.

Next, 2.4 g of BF ₃ diethyl ether complex, 1.6 g of dehydrated methanol, 100 g of polymer A4 and 5 g of toluene were used according to the method of Synthesis Example 4 of WO2015-088021, and a polysilyl group having a fluorosilyl group at the end was used. An oxyalkylene polymer C1-1 (hereinafter referred to as fluorinated polymer C1-1) was obtained. The ¹ H-NMR spectrum of the obtained fluorinated polymer C1-1 (measured in CDCl ₃ solvent using NMR400 manufactured by Shimadzu Co., Ltd.) was measured. As a result, silylmethylene (—CH ₂ ) of the polymer A4 as a raw material was measured. The peak (m, 0.63 ppm) corresponding to -Si) disappeared and a broad peak appeared on the low magnetic field side (0.7 ppm-).

(Synthesis Example 5) Synthesis of crosslinkable silicon group-containing compound E1 that generates an amino group by light 15.3 parts of 2-nitrobenzyl alcohol and 344 parts of toluene were added to a flask and refluxed at about 113 ° C for 60 minutes. Then, 20.5 parts of 3-isocyanatopropyltrimethoxysilane was added dropwise, and the mixture was stirred for 5 hours to obtain a compound (a crosslinkable silicon group-containing compound that generates an amino group by light represented by the following formula (9). Hereinafter, photoaminosilane Generating compound E1) was obtained. As a result of IR spectrum measurement of the photoaminosilane-generating compound E1, no -N = C = O bond was detected.

(Synthesis example 6)
In a stirrer equipped with a thermometer, 589.4 parts by weight of polypropylene glycol (manufactured by Mitsui Chemicals Polyurethane Co., Ltd., trade name: Diol-2000) was dehydrated, and then 4,4-diphenylmethane diisocyanate (MDI) 110. 6 parts by weight was added, and the mixture was reacted at 70 to 90 ° C. for 3 hours under a nitrogen stream to obtain a urethane prepolymer A having an NCO / OH equivalent ratio of 1.5. 0.5 equivalent of 3-mercaptopropyltrimethoxysilane to the urethane prepolymer A is reacted with the urethane prepolymer A, and on average has a trimethoxysilyl group at one end and an NCO group at the other end. A polymer was obtained. With respect to the NCO group of the obtained polymer, an equivalent amount of 4-hydroxybutyl acrylate was reacted with this polymer to obtain a polymer A4 having an average trimethoxysilyl group at one end and an acryloyloxy group at the other end. Obtained.

(Examples 1 to 12 and Comparative Examples 1 to 7)
Each of the blended substances was added at the blending ratio shown in Table 1 and mixed and stirred to prepare a photocurable composition.

In Table 1, the amount of each compounded substance is indicated by g, and the polyoxyalkylene polymers A1 and A2 are the polyoxyalkylene polymers A1 and A2 obtained in Synthesis Examples 1 and 2, respectively, and the acrylic polymer. A3 is the acrylic polymer A3 obtained in Synthesis Example 3, and the organic polymer A4 having a crosslinkable silicon group and a photoradical polymerizable vinyl group in the molecule is the polymer A4 obtained in Synthesis Example 6. The fluorinated polymer C1-1 is the fluorinated polymer C1-1 obtained in Synthesis Example 4, the photoaminosilane-generating compound E1 is the photoaminosilane-generating compound E1 obtained in Synthesis Example 5, and the details of other compounded substances are as follows. It is as follows.
* 1) Photobase generator B1: Irgacure (registered trademark) 379EG [trade name, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4- Morpholinyl) phenyl] -1-butanone] 70% PC (propylene carbonate) solution.
* 2) Photobase generator B2: SA-2 [trade name of San-Apro Co., Ltd.] 5% PC solution.
* 3) Polyfunctional compound D1: 1,6-hexanediol diacrylate, trade name "SR238NS" (manufactured by Sartomer), a bifunctional acrylate monomer.
* 4) Polyfunctional compound D2: trimethylolpropane, trade name "Light acrylate TMP-A" (manufactured by Kyoeisha Chemical Co., Ltd.), trifunctional acrylate monomer.
* 5) Polyfunctional compound D3: dipentaerythritol hexaacrylate, trade name "light acrylate DPE-6A" (manufactured by Kyoeisha Chemical Co., Ltd.), and a hexafunctional acrylate monomer.
* 6) Polyfunctional compound D4: urethane acrylate, trade name "NK Oligo U-15HA" (manufactured by Shin-Nakamura Chemical Co., Ltd.), a polymer having 15 acryloyloxy groups.
* 7) Polyfunctional compound D5: acrylic acrylate, trade name "RC100C" (manufactured by Kaneka Corporation), a polymer having two acryloyloxy groups.
* 8) Monofunctional compound F1: methoxydipropylene glycol acrylate, trade name “Light acrylate DPM-A” (manufactured by Kyoeisha Chemical Co., Ltd.), monofunctional acrylate.
* 9) Monofunctional compound F2: phenoxyethyl acrylate, trade name "Light acrylate PO-A" (manufactured by Kyoeisha Chemical Co., Ltd.).
* 10) Tackifying resin G1: Trade name "Pine Crystal KE-100" (manufactured by Arakawa Chemical Industry Co., Ltd.).
* 11) Epoxy group-containing compound: Bisphenol A type epoxy resin, trade name "JER828" (manufactured by Mitsubishi Plastics, Inc.).
* 12) Cleavage type photoradical generator: trade name "Irgacure (registered trademark) 1173" (BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one.)
* 13) Tin catalyst: 33% PC solution of Neostan U-100 [trade name of Nitto Kasei Co., Ltd.].

The obtained photocurable composition was subjected to a creep test and a tensile shear adhesive strength test by the following methods. The results are shown in Table 1.
1) Creep test The obtained photocurable composition was applied to an adherend [acrylic resin] with an area of 5 mm × 25 mm and a thickness of 100 μm, and UV irradiation [irradiation conditions: UV-LED lamp (wavelength 365 nm, illuminance 1000 mW / cm ² ), integrated light quantity: 3000 mJ / cm ² ]. Immediately after irradiation, the adherend [acrylic resin] is pasted, pressed with a small eye clip, and cured for 30 seconds in a dark room at 23 ° C. and 50% RH, and then subjected to a creep test (weight: 10 g). It was evaluated according to the evaluation criteria.
◯: The adherend did not fall, ×: the adherend fell.

2) Tensile-shear adhesive strength test The obtained photocurable composition was applied to an adherend [acrylic resin] so as to have a thickness of 100 μm, and UV irradiation [irradiation conditions: UV-LED lamp (wavelength 365 nm, The illuminance was 1000 mW / cm ² ), and the integrated light amount was 3000 mJ / cm ² ]. Immediately after the irradiation, an adherend [acrylic resin] was pasted in an area of 25 mm × 25 mm, pressed with a small eye clip, and cured for 3 hours in a dark room at 23 ° C. and 50% RH. After curing, it was measured at a test speed of 50 mm / min in accordance with the tensile shear adhesive strength test method of JIS K6850 rigid adherend. The results are shown in Table 1.

  As can be seen from Table 1, all the photocurable compositions according to Examples 1 to 12 were shown to have a good creep test and to have sufficient tensile shear adhesive strength.

(Examples 13 to 15, Comparative Examples 8 to 11)
Furthermore, each compounded substance was added at the compounding ratio shown in Table 2, and mixed and stirred to prepare a photocurable composition for a liquid gasket.

In Table 2, the blending amount of each blending substance is shown by g, and the polyoxyalkylene polymers A1 and A2 are the polyoxyalkylene polymers A1 and A2 obtained in Synthesis Examples 1 and 2, respectively, and the acrylic polymer. A3 is the acrylic polymer A3 obtained in Synthesis Example 3, and the fluorinated polymer C1-1 is the fluorinated polymer C1-1 obtained in Synthesis Example 4. In addition, compounds with the same annotations as in Table 1 indicate the same compounds as in Table 1. Details of other compounded substances are as follows.
* 14) Photobase generator B3: Irgacure (registered trademark) 379EG (manufactured by BASF, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] ] -1-butanone), diluted with a propylene carbonate solution to 50% by mass for use. In Table 2, the mass part of solid content is described. )
* 15) Polyfunctional compound D6: Light acrylate DPM-A (Kyoeisha Chemical Co., Ltd., trade name, methoxydipropylene glycol acrylate)
* 16) Polyfunctional compound D7: UV3700B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., urethane acrylate, a polymer having two acryloyloxy groups)
* 17) Anti-sagging material: AEROSIL (registered trademark) R972 (manufactured by Nippon Aerosil Co., Ltd., hydrophobic silica)

  The obtained liquid gasket was tested by the following method. Table 2 shows the results.

(Workability test without UV irradiation)
A dispenser robot equipped with a needle having an inner diameter of 0.84 mm as a discharge needle under the condition of 23 ° C. and 50% RH under a fluorescent lamp attached with a film cutting a wavelength of 500 nm or less (hereinafter referred to as “dispenser robot A”) Was used to test the workability of the composition prepared in Example 13 before UV irradiation. In a 23 ° C. and 50% RH environment, the PET film was continuously applied and the time during which the dispense application was possible was measured by touching with a finger.
The case where the work was possible for 8 hours or more was evaluated as "⊚", the case where the work was possible for more than 8 hours and less than 8 hours was evaluated as "○", and the case where the work was impossible due to the nozzle tip being cured within 4 hours was evaluated as "x".

(Shape retention)
Using dispenser robot A, light-cured into a rectangular shape (line width 1 mm) measuring 65.00 mm in length and 18.00 mm in width on the outer periphery of a glass plate having a length of 75.00 mm, a width of 25.00 mm, and a thickness of 2.00 mm. Of the resin composition and UV irradiation [irradiation conditions: UV-LED lamp (wavelength 365 nm, illuminance: 1000 mW / cm ² ), integrated light quantity: 1000 mJ / cm ² , hereinafter referred to as “irradiation condition 1”. ]did. Immediately after irradiation, another glass plate of the same size was attached. Then, in an environment of 23 ° C. and 50% RH, a weight of 500 g was put on and cured for 15 minutes. After curing, compared to the width of the curable composition before laminating, the width is less than twice, "○", less than 3 times, "△", more than 3 times "x" did.

(Initial waterproofness)
Using dispenser robot A, light-cured into a rectangular shape (line width 1 mm) measuring 65.00 mm in length and 18.00 mm in width on the outer periphery of a glass plate having a length of 75.00 mm, a width of 25.00 mm, and a thickness of 2.00 mm. The composition was applied and UV-irradiated (irradiation condition is irradiation condition 1). Immediately after irradiation, another glass plate of the same size was attached. Then, in an environment of 23 ° C. and 50% RH, a weight of 500 g was put on and cured for 15 minutes. After the curing, the glass plates laminated and stuck together were immersed in a water tank having a water depth of 1.0 m for 30 minutes, and it was visually determined whether or not water entered the inside of the gasket. It was evaluated as "○" when there was no intrusion of water and "x" when there was intrusion of water. Comparative Example 8 was cured to a state where it could not be bonded, and Comparative Examples 10 and 11 were uncured and could not be evaluated.

(Initial peelability)
Using dispenser robot A, light-cured into a rectangular shape (line width 1 mm) measuring 65.00 mm in length and 18.00 mm in width on the outer periphery of a glass plate having a length of 75.00 mm, a width of 25.00 mm, and a thickness of 2.00 mm. The composition was applied and UV-irradiated (irradiation condition is irradiation condition 1). Immediately after irradiation, another glass plate of the same size was attached. Then, in an environment of 23 ° C. and 50% RH, a weight of 500 g was put on and cured for 1 minute. After curing, the glass plates laminated and stuck together were peeled off and broken between the glass and the adhesive. The failure at the interface of the glass plate was evaluated as "○", and the cohesive failure of the adhesive was evaluated as "x". Comparative Example 8 was cured to a state where it could not be bonded, and Comparative Examples 9 to 11 were uncured and could not be evaluated.

(Water resistance of peeled liquid gasket)
Using dispenser robot A, light-cured into a rectangular shape (line width 1 mm) measuring 65.00 mm in length and 18.00 mm in width on the outer periphery of a glass plate having a length of 75.00 mm, a width of 25.00 mm, and a thickness of 2.00 mm. The composition was applied and UV-irradiated (irradiation condition is irradiation condition 1). Immediately after the irradiation, another glass plate of the same size was attached and cured for 1 minute. After that, the glass plates laminated and laminated were peeled off once and then laminated again. After pasting again, under a 23 ° C. and 50% RH environment, a weight of 500 g was put on and cured for 15 minutes. After the curing, the glass plates laminated and stuck together were immersed in a water tank having a water depth of 1.0 m for 30 minutes, and it was visually determined whether or not water entered the inside of the gasket. It was evaluated as "○" when there was no intrusion of water and "x" when there was intrusion of water. Note that Comparative Example 8 was cured to a state where it could not be laminated, and Comparative Examples 9 to 11 were uncured after curing for 1 minute and could not be peeled off cleanly from both glass plates, and therefore were not evaluated.

(Peelability after curing)
Using dispenser robot A, light-cured into a rectangular shape (line width 1 mm) measuring 65.00 mm in length and 18.00 mm in width on the outer periphery of a glass plate having a length of 75.00 mm, a width of 25.00 mm, and a thickness of 2.00 mm. The composition was applied and UV-irradiated (irradiation condition is irradiation condition 1). Immediately after irradiation, another glass plate of the same size was attached. Then, in an environment of 23 ° C. and 50% RH, a weight of 500 g was put on and cured for 1 day. After curing, the glass plates laminated and stuck together were peeled off and broken between the glass and the adhesive. The failure at the interface of the glass plate was evaluated as "○", and the cohesive failure of the adhesive was evaluated as "x". Comparative Example 8 was cured to a state where it could not be bonded, and Comparative Examples 10 and 11 were uncured and could not be evaluated.

(Examples 14 to 15, Comparative Examples 8 to 11)
As shown in Table 2, a photocurable composition and a curable composition were prepared in the same manner as in Example 13 except that the compounding substances were changed. Then, in the same manner as in Example 13, a curability test and an adhesion test of the photocurable composition were performed. The results are shown in Table 2.

  The liquid gaskets of Comparative Examples 9 to 11 had poor shape-retaining properties, were wet and spread when the glass plates were laminated, and could not be used as gaskets.

  As shown in Table 2, the liquid gaskets according to the examples do not cure when not irradiated with active energy rays and have excellent shape retention, and have sufficient bonding time after irradiation with active energy rays. It was shown that Further, in the housing member joined by using the liquid gasket according to the example, the housing member can be removed with a small force even at the initial stage of curing and after curing without protruding to a portion where sealing is not desired. It was shown that the housing member can be rejoined using the gasket as it is, and the initial sealing performance such as waterproof performance is maintained even after the rejoining.

Claims (12)

(A) a crosslinkable silicon group-containing organic polymer,
(B) a photobase generator,
A polyoxyalkylene polymer having a (C1 -1) terminus fluoro silyl group,
(D) A photocurable composition containing a polyfunctional compound having more than one (meth) acryloyl group in one molecule.   The photocurable composition according to claim 1, further comprising (E) a crosslinkable silicon group-containing compound that produces one or more amino groups selected from the group consisting of primary amino groups and secondary amino groups by light. Composition.   The photocurable composition according to claim 1, further comprising (F) a monofunctional compound having a photopolymerizable unsaturated group.   The photocurable composition according to claim 1, further comprising (G) a tackifying resin.   The (A) crosslinkable silicon group-containing organic polymer is at least one selected from the group consisting of a crosslinkable silicon group-containing polyoxyalkylene polymer and a crosslinkable silicon group-containing (meth) acrylic polymer. The photocurable composition according to any one of claims 1 to 4.   The photocurable composition according to any one of claims 1 to 5, wherein the photobase generator (B) is a photolatent tertiary amine.   The (A) organic polymer having a crosslinkable silicon group is (a-1) a polymer having a crosslinkable silicon group and a photoradical-polymerizable vinyl group in the molecule (provided that it has a Si-F bond. And (a-2) and (a-2) are one or more polymers selected from the group consisting of organic polymers having a crosslinkable silicon group other than (a-1). Sex composition.   A cured product formed by irradiating the photocurable composition according to any one of claims 1 to 7 with light.   A product manufactured using the photocurable composition according to any one of claims 1 to 7.   A product using the photocurable composition according to any one of claims 1 to 7 as an adhesive.   An electronic device product comprising the photocurable composition according to claim 1. A method of reworking an electronic device,
Polyoxy having (i) a said site forming type liquid gasket electronics, and (A) a crosslinkable silicon group-containing organic polymer, and (B) a photobase generator, a fluoroalkyl silyl group (C1 -1) end A step of preparing an in-situ moldable liquid gasket containing an alkylene polymer and (D) a polyfunctional compound having more than one (meth) acryloyl group in one molecule;
(B) a step of applying the liquid gasket in an uncured state to a portion of one housing member of an electronic device to be sealed, irradiating with active energy rays, and sandwiching the other housing member;
(C) A method of reworking an electronic device, comprising a step of removing a housing member of the electronic device that requires reworking after curing and replacing internal parts.