JP2018030989A - Photocurable composition, cured composition-containing product, sticking method, and method for producing product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable composition that can be applied to various adherends, and is stuck after UV irradiation to immediately exhibit sufficient adhesion, and a cured composition-containing product, a sticking method, and a method for producing a product.SOLUTION: A photocurable composition contains (A) monoacrylate that suppresses oxygen inhibition, such as 2-hydroxy-3-phenoxypropyl (meth) acrylate or a derivative thereof, which may contain a substituent in an aromatic ring, (B) a crosslinkable silicon group-containing polymer, and (C) a photoinitiator.SELECTED DRAWING: None

Description

  The present invention relates to a photocurable composition, a cured composition-containing product, a bonding method, and a product manufacturing method. In particular, the present invention relates to a photocurable composition, a cured composition-containing product, a laminating method, and a method for producing a product that can be cured in a short time and have excellent rising adhesiveness.

  An organic polymer having a hydroxyl group or hydrolyzable group bonded to a silicon atom and having a silicon-containing group that can be crosslinked by forming a siloxane bond (hereinafter also referred to as “crosslinkable silicon group”) is obtained at room temperature. It is also known that the rubber has a property that a rubber-like cured product can be obtained by crosslinking by formation of a siloxane bond accompanied by hydrolysis reaction of a crosslinkable silicon group due to moisture or the like. Among these polymers having a crosslinkable silicon group, organic polymers whose main chain skeleton is a polyoxyalkylene polymer or a (meth) acrylic acid ester polymer are used for sealing materials, adhesives, paints, etc. Widely used.

  The curable composition used for sealing materials, adhesives, paints, etc. and the rubber-like cured product obtained by curing have various properties such as curability, adhesiveness, storage stability, mechanical properties such as modulus, strength, and elongation. Properties are required, and many studies have been made on organic polymers containing crosslinkable silicon groups. In recent years, rapid curing is required in various fields such as an electronic component / electronic device assembling field, but in the case of a moisture-curing adhesive, there is a problem that a bonding time after application is shortened.

  On the other hand, as a photocrosslinkable composition using an organic polymer containing a crosslinkable silicon group, Patent Document 1 discloses a polymer having two or more hydrolyzable silyl groups in one molecule, and the polymer by light irradiation. A photocrosslinkable composition comprising a compound that crosslinks a compound, and a compound containing a compound that generates an acid or a base upon irradiation with light as a compound that crosslinks a polymer by light irradiation. The crosslinkable composition is illustrated (patent document 1, claims 1-3).

  However, in the composition described in Patent Document 1, when a photoacid generator is used as a compound that crosslinks a polymer by light irradiation, for example, an active acid generated from the photoacid generator when amines, alkaline substances, and the like are mixed. The catalyst reacts and photocationic polymerization is significantly inhibited. This is likely to occur when a basic substance is contained in the adherend, as well as when a basic adhesion-imparting agent, filler or the like is blended in the composition. Therefore, adhesiveness is also poor and adherends are limited. Moreover, there exists a problem of producing a rust, and it cannot apply to metal adhesion. In addition, when a photobase generator is used as a compound that crosslinks a polymer by light irradiation, there is a problem that the efficiency is low and a long time is required for irradiation time and curing.

  Patent Document 2 describes an adhesive composition containing a polymerizable acrylate, a silane-terminated polymer, a photoinitiator, and a photoacid generator. According to the adhesive composition described in Patent Document 2, it is possible to quickly make a B-stage after ultraviolet irradiation, and problems such as slumping can be avoided. However, in the adhesive composition described in Patent Document 2, as described in Examples of Patent Document 2, sufficient adhesive force is not exhibited immediately after UV irradiation.

  Patent Document 3 discloses a photopolymerizable mixed monomer comprising (A) an alkyl (meth) acrylate having 4 to 14 carbon atoms of an alkyl group, (B) a carboxyl group-containing vinyl monomer, and (C) a photopolymerizable initiator. For 100 parts by weight, (D) after coating a photopolymerizable composition containing 5 to 50 parts by weight of a crosslinkable polymer having at least two alkoxysilyl groups in the molecule on at least one surface of the substrate, An acrylic pressure-sensitive adhesive tape obtained by photopolymerization is described. However, in the acrylic pressure-sensitive adhesive tape described in Patent Document 3, it is necessary to apply a photopolymerizable composition to a PET film and cover the exposed surface of the photopolymerizable composition with the PET film when UV-checked. It takes time and effort.

JP 2001-172514 A Special table 2009-530441 JP-A-9-137137

  In the composition described in each of the above patent documents, the composition is cured before light irradiation, or when it is irradiated with light, it is necessary to block the composition from outside air with a PET film or the like. In addition to limiting the targets to which the adhesive composition can be applied, the number of work steps is increased in order to obtain a cured product having adhesiveness, which takes time and effort.

  Accordingly, the object of the present invention can be applied to various adherends, and can be applied to a photocurable composition, a cured composition-containing product, and a bonded product that immediately exhibit sufficient adhesive force when bonded after UV irradiation. It is an object to provide a method and a method for manufacturing a product.

  In order to achieve the above object, the present invention provides (A) a monoacrylate represented by the following general formula (1), which suppresses oxygen inhibition, (B) a crosslinkable silicon group-containing polymer, and (C) photoinitiation. A photocurable composition containing an agent is provided.

In general formula (1), R ¹ represents —H or —CH ₃ , and R ^{2 to} R ⁶ each independently represent a hydrogen atom, a nitro group, a cyano group, a hydroxy group, a halogen atom, an acetyl group, or a carbonyl group. A group, a substituted or unsubstituted allyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, a heterocyclic structure-containing group, and a plurality of The substituent includes at least one group selected from the group consisting of groups having a ring. At least two groups selected from the group consisting of R ^{2 to} R ⁶ may be bonded to each other to form a cyclic structure together with the carbon atom to which they are bonded.

  The photocurable composition may further contain (D) a compound having a Si—F bond and at least one compound selected from the group consisting of boron trifluoride.

  Moreover, the said photocurable composition can also contain (E) tackifying resin further.

  Moreover, the said photocurable composition can also contain (F) polyfunctional (meth) acrylate further.

  In the photocurable composition, the polyfunctional (meth) acrylate (F) may be a polyfunctional polymer containing a photoradically polymerizable vinyl group.

  Moreover, in order to achieve the said objective, this invention provides the hardening composition containing product comprised using the photocurable composition as described in any one of said.

  In addition, the present invention is a bonding method in which a plurality of adherends are bonded to achieve the above object, and the photocurable composition according to any one of the above is applied to at least one adherend. An application step for applying, a light irradiation step for irradiating the photocurable composition applied to one adherend, and a photocurable composition applied to one adherend and irradiated with light. There is provided a bonding method including a bonding step of sandwiching between the other adherends.

  In order to achieve the above object, the present invention provides a method for producing a product having a plurality of adherends, wherein at least one of the photocurable compositions described in any one of the above is provided. A coating step for applying to one adherend, a light irradiation step for irradiating light to a photocurable composition applied to one adherend, and a light applied to one adherend and irradiated with light. There is provided a manufacturing method of a product including an adhesion step of sandwiching and adhering a curable composition between the other adherends.

  According to the photocurable composition, the cured composition-containing product, the laminating method, and the manufacturing method of the product according to the present invention, it can be applied to various adherends. It is possible to provide a photocurable composition, a cured composition-containing product, a laminating method, and a product manufacturing method that exhibit sufficient adhesive strength.

  The photocurable composition according to the present invention is a photocurable composition that quickly exhibits tackiness upon irradiation with light such as active energy rays and is post-cured (that is, formed into an adhesive). That is, the photocurable composition has (A) a compound capable of exhibiting cohesive force and suppressing oxygen inhibition by oxygen in the environment, and (B) a hydroxyl group or a hydrolyzable group bonded to a silicon atom, A polymer having a silicon-containing group that can be crosslinked by forming a siloxane bond (hereinafter also referred to as “crosslinkable silicon group”), (C) a compound that generates a base by light irradiation, and (D) Si— And a compound having an F bond and at least one compound selected from the group consisting of trifluoride compounds.

  Specifically, the photocurable composition of the present invention comprises (A) a monoacrylate represented by the following general formula (1), (B) a crosslinkable silicon group-containing polymer, and (C) a photobase generator. And (D) a compound having a Si—F bond, and at least one compound selected from the group consisting of boron trifluoride. Moreover, the photocurable composition of the present invention may further contain (E) a tackifying resin. Furthermore, the photocurable composition of the present invention further comprises (F) a polyfunctional monomer containing a photoradically polymerizable vinyl group and / or (F) a polyfunctional polymer containing a photoradically polymerizable vinyl group. You can also

In General Formula (1), R ¹ represents —H or —CH ₃ , and R ^{2 to} R ⁶ each independently represent a hydrogen atom or a substituent. Examples of the substituent include a nitro group, a cyano group, a hydroxy group, a halogen atom, an acetyl group, a carbonyl group, a substituted or unsubstituted allyl group, and a substituted or unsubstituted alkyl group (preferably having 1 to 5 carbon atoms). An alkyl group), a substituted or unsubstituted alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, a heterocyclic structure-containing group, and a plurality of rings. And a combination thereof. Any of R ^{2 to} R ⁶ may be bonded to each other to form a cyclic structure. When at least two groups selected from the group consisting of R ^{2 to} R ⁶ are bonded to each other to form a cyclic structure, a structure in which a plurality of benzene rings are condensed, a benzene ring and a heterocyclic ring or a non-aromatic ring, A structure in which a ring to which a functional group such as a carbonyl group is bonded may be formed. Among these substituents, a substituted or unsubstituted alkyl group is preferable, and a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms is more preferable.

(A component: monoacrylate)
The component A contained in the photocurable composition is a compound having a plurality of electron-withdrawing groups, and is a compound in which active radicals are easily generated in a portion sandwiched between the plurality of electron-withdrawing groups. The present inventors presume that a compound having such a structure can suppress the inhibition of polymerization by oxygen, and as a result of studying the characteristics of the photocurable composition using various compounds, It has been found that the component A of the composition is suitable. That is, as the component A, a secondary hydroxyl group disposed in a portion sandwiched between a plurality of —CH ₂ groups (specifically, two —CH ₂ groups) and an electron-withdrawing group located at both ends of the molecule It has been found that monofunctional compounds are preferred. Specifically, examples of the component A include monoacrylates represented by the general formula (1). Specific examples of the component A include 2-hydroxy-3-phenoxypropyl acrylate. In addition, it is relatively lower than the glass transition temperature of epoxy acrylate, acrylamide, etc. from the viewpoint of making the cured product obtained from the photocurable composition more flexible than the cured product obtained from epoxy acrylate, acrylamide, etc. From the viewpoint of using a compound having a glass transition temperature, the component A is preferably not monofunctional but monoacrylate.

  In addition, the following mechanisms are estimated as a mechanism which suppresses the superposition | polymerization inhibition by oxygen. That is, in radical polymerization, polymerization inhibition by oxygen occurs and the monomer reaction rate decreases. In particular, the reaction rate decreases in the surface layer that comes into contact with air. Oxygen inhibition is caused by the polymerization reaction being stopped by the low polymerization ability of peroxyl radicals generated by trapping the radicals generated by polymerization of radicals initiated from photoinitiators and polymerization terminal radicals in oxygen. Here, in the case where the component A monoacrylate having a function as a chain transfer agent is present in the system, the peroxy radical having hydrogen abstraction ability extracts hydrogen from the monoacrylate, so that α of the newly generated secondary hydroxyl group is α. It is thought that carbon radicals initiate polymerization. In addition, since the α-carbon radical of the secondary hydroxyl group produced can supplement oxygen, an effect of reducing the oxygen concentration in the system can be considered. It is speculated that oxygen inhibition is suppressed by these mechanisms.

In addition, when the monoacrylate containing a crosslinkable silicon group is used as the monoacrylate, the photocurable composition becomes sticky by light irradiation, and is easily post-cured (adhesive) due to a change with time. When a liquid organic polymer is used as the crosslinkable silicon group-containing polymer, the liquid organic polymer becomes a monoacrylate containing a crosslinkable silicon group by introducing a crosslinkable silicon group as a substituent. Specific structures of the crosslinkable silicon group include a trialkoxysilyl group [—Si (OR) ₃ ] such as a trimethoxysilyl group and a dialkoxysilyl group [—Si (CH ₃ ) (OR) such as a methyldimethoxysilyl group. 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.

(B component: crosslinkable silicon group-containing polymer)
The crosslinkable silicon group-containing polymer is not particularly limited as long as it is an organic polymer having a crosslinkable silicon group (hereinafter referred to as “crosslinkable silicon group-containing organic polymer”). In the present invention, the main chain is an organic polymer that is not polysiloxane, and the organic polymer having various main chain skeletons excluding polysiloxane is preferable in that it does not contain or generate a low-molecular cyclic siloxane that causes contact failure. It is. Further, an organic polymer having a crosslinkable silicon group that is difficult to break the main chain, has good compatibility, and is easy to blend with an adhesion-imparting agent or the like is also preferable.

  Specific examples of the main chain skeleton of the crosslinkable silicon group-containing organic polymer include polyoxyalkylene polymers such as polyoxypropylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer; ethylene- Propylene copolymers, polyisobutylene, polyisoprene, polybutadiene, hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; dibasic acids such as adipic acid and glycols Polyester polymer obtained by condensation with lactones or ring-opening polymerization of lactones; (meth) acrylic acid ester polymer obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate ; (Meth) acrylic acid ester monomers, vinyl acetate, acrylonitrile , Vinyl polymers obtained by radical polymerization of monomers such as styrene; graft polymers obtained by polymerizing vinyl monomers in organic polymers; polysulfide polymers; polyamide polymers; polycarbonate polymers; Examples include diallyl phthalate polymers. These skeletons may be contained alone in the crosslinkable silicon group-containing organic polymer, or two or more kinds may be contained in blocks or randomly.

  Furthermore, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester polymers can be obtained with a relatively low glass transition temperature. The cured product is preferable because it is excellent in cold resistance. Polyoxyalkylene polymers and (meth) acrylic acid ester polymers are particularly preferred because they have high moisture permeability and are excellent in deep part curability when made into a one-component composition.

  As the crosslinkable silicon group of the crosslinkable silicon group-containing organic polymer, for example, a group represented by the general formula (2) is preferable.

In formula (2), R ⁷ represents an organic group. R ⁷ is preferably a hydrocarbon group having 1 to 20 carbon atoms. Among these, R ⁷ is particularly preferably a methyl group. R ⁷ may have a substituent. When two or more R ⁷ are present, the plurality of R ⁷ may be the same or different. W represents a hydroxyl group or a hydrolyzable group, and when two or more W exist, the plurality of W may be the same or different. a is an integer of 0, 1, 2, or 3. In order to obtain a photocurable composition having a sufficient curing rate in consideration of curability, a in formula (2) is preferably 2 or more, and more preferably 3.

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

  The hydrolyzable group represented by W is not particularly limited as long as it is other than F atom. Examples thereof include an alkoxy group, an acyloxy group, a ketoximate group, an aminooxy group, and an alkenyloxy group. An alkoxy group is preferable from the viewpoint of mild hydrolysis and easy handling. Among the alkoxy groups, those having a smaller number of carbon atoms have higher reactivity, and the reactivity increases as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group. Although it can be selected according to the purpose and use, a methoxy group or an ethoxy group is usually used.

Specific examples of the crosslinkable silicon group include trialkoxysilyl groups [—Si (OR) ₃ ] such as trimethoxysilyl group and triethoxysilyl group, dialkoxy such as methyldimethoxysilyl group and methyldiethoxysilyl group. A silyl group [—SiR ¹ (OR) ₂ ] can be mentioned, 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.

  Moreover, a crosslinkable silicon group may be used by 1 type and may be used together 2 or more types. The crosslinkable silicon group can be present in the main chain, the side chain, or both.

  The organic polymer having a crosslinkable silicon group may be linear or branched, and its number average molecular weight is about 500 to 100,000 in terms of polystyrene in GPC, more preferably 1,000 to 50,000. And particularly preferably 3,000 to 30,000. If the number average molecular weight is less than 500, the cured product tends to be inconvenient in terms of elongation characteristics, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity.

  In order to obtain a rubber-like cured product having high strength, high elongation, and low elastic modulus, the average number of crosslinkable silicon groups contained in the organic polymer is 0.8 or more, preferably in one molecule of the polymer. Is 1.0 or more, more preferably 1.1 to 5. If the average number of crosslinkable silicon groups contained in the molecule is less than 0.8, the curability becomes insufficient and it becomes difficult to exhibit good rubber elastic behavior. The crosslinkable silicon group may be present at the end of the main chain of the organic polymer molecular chain, at the end of the side chain, or both. 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 is increased, so that the high strength, high elongation, A rubber-like cured product having a low elastic modulus is easily obtained.

The polyoxyalkylene polymer is essentially a polymer having a repeating unit represented by the general formula (3).
-R ⁸ -O- ··· (3)
In General Formula (3), R ⁸ is a linear or branched alkylene group having 1 to 14 carbon atoms, preferably a linear or branched alkylene group having 1 to 14 carbon atoms, and having 2 to 4 carbon atoms. The linear or branched alkylene group is more preferable.

Specific examples of the repeating unit represented by the general formula (3) include —CH ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) 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 type of repeating unit, or may be composed of two or more types of repeating units.

  Examples of the synthesis method of the polyoxyalkylene polymer include, but are not particularly limited to, a polymerization method using an alkali catalyst such as KOH, a polymerization method using a double metal cyanide complex catalyst, and the like. According to the polymerization method using a double metal cyanide complex catalyst, a polyoxyalkylene polymer having a number average molecular weight of 6,000 or more and a high molecular weight of 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 are obtained from a reaction between an aromatic polyisocyanate such as toluene (tolylene) diisocyanate and diphenylmethane diisocyanate; an aliphatic polyisocyanate such as isophorone diisocyanate and a polyoxyalkylene polymer having a hydroxyl group. 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 the molecule is added with a compound having a functional group reactive to this functional group and a crosslinkable silicon group. By reacting, a crosslinkable silicon group can be introduced into the polyoxyalkylene polymer (hereinafter referred to as polymer reaction method).

  As a specific example of the polymer reaction method, a hydrosilane or mercapto compound obtained by allowing a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to act on an unsaturated group-containing polyoxyalkylene polymer to form a crosslinkable silicon group The method of obtaining the polyoxyalkylene type polymer which has can be mentioned. An unsaturated group-containing polyoxyalkylene-based polymer is obtained by reacting an organic polymer having a functional group such as a hydroxyl group with an organic compound having an active group and an unsaturated group that are reactive with the functional group. A polyoxyalkylene polymer containing can be obtained.

  Other specific examples of the polymer reaction method include a method of reacting a polyoxyalkylene polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a crosslinkable silicon group, or a polyoxyalkylene having an isocyanate group at a terminal. Examples thereof include a method of reacting an alkylene polymer with a compound having an active hydrogen group such as a hydroxyl group or an amino group and a crosslinkable silicon group. When an isocyanate compound is used, a polyoxyalkylene polymer having a crosslinkable silicon group can be easily obtained.

  The polyoxyalkylene polymer having a crosslinkable silicon group may be used alone or in combination of two or more.

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

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

  The saturated hydrocarbon polymer having a crosslinkable silicon group may be used alone or in combination of two or more.

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

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

  These may be used alone or may be copolymerized. Furthermore, the number of 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 polymer comprising a methacrylic acid ester monomer is particularly preferred because of its good adhesion. In addition, when the viscosity is reduced, the flexibility is imparted, and the tackiness is imparted, it is preferable to use an acrylate monomer as appropriate. In addition, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  The production method of the (meth) acrylic acid ester polymer is not particularly limited, and for example, a radical polymerization method using a radical polymerization reaction can be used. The radical polymerization method includes a radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator, or a controlled radical capable of introducing a reactive silyl group at a controlled position such as a terminal. A polymerization method 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 a high viscosity. Therefore, when obtaining a (meth) acrylate polymer having a narrow molecular weight distribution and low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high rate, It is preferable to use a controlled radical polymerization method.

  Examples of the controlled radical polymerization method include a free radical polymerization method and a living radical polymerization method using a chain transfer agent having a specific functional group, and an addition-fragmentation chain transfer (RAFT) polymerization method, Living radical polymerization methods such as a radical polymerization method using a transition metal complex (Transition-Metal-Mediated Living Radical Polymerization) are 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 may be used alone or in combination of two or more.

  These organic polymers having a crosslinkable silicon group may be used alone or in combination of two or more. Specifically, a group consisting of a polyoxyalkylene polymer having a crosslinkable silicon group, a saturated hydrocarbon polymer having a crosslinkable silicon group, and a (meth) acrylic acid ester polymer having a crosslinkable silicon group. An organic polymer obtained by blending two or more selected from the above can also be used.

There are various methods 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. For example, it has a crosslinkable silicon group and the molecular chain is substantially the general formula (4):
—CH ₂ —C (R ⁹ ) (COOR ¹⁰ ) — (4)
(Wherein R ⁹ represents a hydrogen atom or a methyl group, R ¹⁰ represents an alkyl group having 1 to 5 carbon atoms) and a general formula (5):
—CH ₂ —C (R ⁹ ) (COOR ¹¹ ) — (5)
(Wherein R ⁹ is the same as described above, and R ¹¹ represents an alkyl group having 6 or more carbon atoms) A copolymer composed of a (meth) acrylate monomer unit is represented by a crosslinkable silicon group And a method of blending and producing a polyoxyalkylene-based polymer having.

R ^{10 in the} general formula (4) is, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, etc. having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms, Preferably, an alkyl group having 1 to 2 carbon atoms is used. The alkyl group of R ¹⁰ may alone, or may be a mixture of two or more.

R ^{11 in the} general formula (5) is, for example, a 2-ethylhexyl group, lauryl group, stearyl group or the like having 6 or more carbon atoms, usually 7 to 30 carbon atoms, preferably 8 to 20 carbon atoms long. Chain alkyl groups. The alkyl group of R ¹¹ is same as in the case of R ^10, may be alone or in admixture.

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

  The number average molecular weight of the (meth) acrylic acid ester polymer is preferably 600 to 10,000, more preferably 600 to 5,000, and still more preferably 1,000 to 4,500. By setting the number average molecular weight within this range, 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. The compounding ratio of the polyoxyalkylene polymer having a crosslinkable silicon group and the (meth) acrylic acid ester polymer having a crosslinkable silicon group is not particularly limited, but the (meth) acrylic acid ester polymer and It is preferable that the (meth) acrylic acid ester polymer is in the range of 10 to 60 parts by mass, more preferably in the range of 20 to 50 parts by mass with respect to 100 parts by mass in total with the polyoxyalkylene polymer. More preferably, it is 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 is increased, and workability is deteriorated.

  Furthermore, 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, in the presence of an organic polymer having a crosslinkable silicon group, A method of polymerizing a (meth) acrylic acid ester monomer can be used.

  When blending two or more kinds of polymers, the saturated hydrocarbon polymer having a crosslinkable silicon group and / or the crosslinkability with respect to 100 parts by mass of the polyoxyalkylene polymer having a crosslinkable silicon group. It is preferable to use 10 to 200 parts by mass of the (meth) acrylic acid ester-based polymer having a silicon group, and it is more preferable to use 20 to 80 parts by mass.

  The blending ratio of the (A) monoacrylate and the (B) crosslinkable silicon group-containing polymer is preferably 10 to 80 parts by mass, more preferably 20 to 70 parts by mass with respect to 100 parts by mass in total of the A component and the B component. 30 to 60 parts by mass is most preferable. From the viewpoint of ensuring the strength of the cured film at the time of bonding within a range where the adhesive strength is sufficiently exhibited and ensuring sufficient crosslinking after moisture curing, (A) monoacrylate and (B) crosslinking The blending ratio of the functional silicon group-containing polymer is preferably 10 parts by mass or more, and from the viewpoint of exhibiting the inhibitory effect of oxygen inhibition by the component A and exhibiting sufficient adhesive force during bonding, (A) monoacrylate and ( B) The blending ratio of the crosslinkable silicon group-containing polymer is preferably 80 parts by mass or less.

(C component: photoinitiator)
As the photoinitiator, a photoradical generator and / or a photobase generator can be used. The photo radical generator is a compound that generates radicals by irradiation with active energy rays such as ultraviolet rays and electron beams. Examples of the photoradical generator include benzoin ether derivatives, benzophenones, acetophenones, oxime ketones, acylphosphine oxides, titanocenes, thioxanthones, quinones, and derivatives obtained by increasing their molecular weight. .

  The photobase generator acts as a curing catalyst for the (B) crosslinkable silicon group-containing organic polymer when irradiated with light. The photobase generator generates bases and radicals by the action of active energy rays such as ultraviolet rays, electron beams, 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. (2) Decomposed amines by decomposition by intramolecular nucleophilic substitution reaction or rearrangement reaction. A known photobase generator such as a compound to be released, or (3) a compound that causes a predetermined chemical reaction to emit a base upon irradiation with energy rays such as ultraviolet rays, visible light, and infrared rays can be used. A radical generated from the photobase generator has a function of curing the A component, and a base generated from the photobase generator has a function of curing the B component.

  As the base generated from the photobase generator, for example, an organic base such as an amine compound is preferable. For example, primary alkylamines described in WO2015-088021 (hereinafter also referred to as “Document 1”), Primary aromatic amines, secondary alkyl amines, amines having secondary amino groups and tertiary amino groups, tertiary alkyl amines, tertiary heterocyclic amines, tertiary aromatic amines , Amidines and phosphazene derivatives. Of these, amine compounds having a tertiary amino group are preferred, and amidines and phosphazene derivatives which are strong bases are more preferred. 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 Document 1.

  Among the non-cyclic amidine compounds, for example, a photobase generator that generates an aryl-substituted guanidine compound or an aryl-substituted biguanide compound described in Document 1 is used as a catalyst for (B) a crosslinkable silicon group-containing organic polymer. When used, it is preferable because it shows a tendency to improve the curability of the surface, and a tendency to improve the adhesion of the resulting cured product.

  Examples of cyclic amidines include cyclic guanidine compounds, imidazoline compounds, imidazole compounds, tetrahydropyrimidine compounds, triazabicycloalkene compounds, and diazabicycloalkene compounds described in Document 1.

  Among the cyclic amidines, 1,8-diazabicyclo [5.4.0] undecene is obtained from the point that it is easily available industrially and the pKa value of the conjugate acid is 12 or more and exhibits high catalytic activity. -7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) is particularly preferred.

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

  Examples of photolatent primary amines and photolatent secondary amines include orthonitrobenzyl urethane compounds described in Document 1, dimethoxybenzyl urethane compounds, benzoins carbamates, o-acyl oximes, o- Carbamoyl oximes; N-hydroxyimide carbamates; formanilide derivatives; aromatic sulfonamides; cobalt amine complexes and the like.

  Examples of photolatent tertiary amines include α-aminoketone derivatives, α-ammonium ketone derivatives, benzylamine derivatives, benzylammonium salt derivatives, α-aminoalkene derivatives, α-ammonium alkene derivatives, and amine imides described in Document 1. Benzyloxycarbonylamine derivatives that generate amidine by light, salts of carboxylic acid and tertiary amine, 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), etc., a tertiary amine composed of one nitrogen atom Examples include α-aminoketone compounds that generate tertiary amines having a group.

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

  Examples of benzylamine derivatives include 5-benzyl-1,5-diazabicyclo [4.3.0] nonane and 5- (anthracen-9-yl-methyl) -1,5-diazabicyclo [4.3.0]. Nonane, benzylamine derivatives such as 5- (naphth-2-yl-methyl) -1,5-diazabicyclo [4.3.0] nonane, and the like can be mentioned.

  Examples of benzylammonium salt derivatives include (9-anthryl) methyl 1-azabicyclo [2.2.2] octanium tetraphenylborate, 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 benzyloxycarbonylamine derivatives that generate amidine by light include benzyloxycarbonylimidazoles, benzyloxycarbonylguanidines, and diamine derivatives described in Document 1.

  Examples of the salt of carboxylic acid and tertiary amine include α-ketocarboxylic acid ammonium salt and carboxylic acid ammonium salt described in Document 1.

  Among photobase generators, photolatent tertiary amines are preferred from the viewpoint of the high catalytic activity of the generated base, and benzylammonium is preferred because of high base generation efficiency and good storage stability as a composition. Salt derivatives, benzyl-substituted amine derivatives, α-aminoketone derivatives and α-ammonium ketone derivatives are preferred. In particular, an α-aminoketone derivative and an α-ammonium ketone derivative are more preferable because the base generation efficiency is better, and an α-aminoketone derivative is more preferable than the solubility in the blend. Of the α-aminoketone derivatives, α-aminoketone compounds in which the base generated from the basic strength of the generated base is an amidine are preferred, and a tertiary amine group composed of one nitrogen atom is more easily available. Examples include α-amino ketone compounds that generate tertiary amines.

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

(D component: silicon compound having Si-F bond)
(D) As the silicon compound having a Si—F bond, various compounds including a silicon group having a Si—F bond (hereinafter sometimes referred to as a fluorosilyl group) can be used. As the silicon compound of component (D), both inorganic compounds and organic compounds can be used, and there is no particular limitation, and any of low molecular compounds and high molecular compounds can be used. As the component (D), an organic compound having a fluorosilyl group is preferable in the present invention, and an organic polymer having a fluorosilyl group is more preferable because of high safety. Moreover, the low molecular organosilicon compound which has a fluoro silyl group from the point from which a photocurable composition becomes low viscosity is preferable.

  (D) Specifically, as a silicon compound having a Si—F bond, fluorosilanes described in Document 1 represented by Formula (6), and fluorosilyl groups described in Document 1 represented by Formula (7) are used. Preferred examples include a compound having a fluorosilyl group (hereinafter also referred to as a fluorinated compound) and an organic polymer having a fluorosilyl group described in Reference 1 (hereinafter also referred to as a fluorinated polymer).

R ¹² _4-d SiF _d (6)
(In Formula (6), R ¹² is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ¹³ SiO— (R ¹³ is each independently having 1 to 20 carbon atoms. Or a substituted or unsubstituted hydrocarbon group, or a fluorine atom), d is any one of 1 to 3, and d is preferably 3. R ¹² And when there are a plurality of R ^{13 s} , they may be the same or different.)

-SiF _d R ¹² _e Z _f (7)
(In Formula (7), R < ¹² > and d are respectively the same as Formula (6), Z is respectively independently the other hydrolysable group except a hydroxyl group or a fluorine, and e is either 0-2. F is any one of 0 to 2, and d + e + f is 3. When a plurality of R ¹² , R ¹³ and Z are present, they may be the same or different.

  Examples of the fluorosilanes represented by the formula (6) include the fluorosilanes represented by the formula (6). Examples thereof include fluorodimethylphenylsilane, vinyl trifluorosilane, γ-methacryloxypropyl trifluorosilane, octadecyl trifluorosilane, and the like.

In the compound having a fluoroalkyl silyl group represented by the formula (7), the hydrolyzable group represented by Z, an alkoxy group is preferable from the viewpoint of hydrolyzability and easy handling at moderate, as R ¹² is a methyl group preferable. Further, as the hydrolyzable group, an alkenyloxy group is preferable, and an alkoxy group is particularly preferable from the viewpoint of mild hydrolyzability and easy handling.

When the fluorosilyl group represented by Formula (7) is illustrated, the silicon group which does not have a hydrolysable group other than a fluorine, and the fluorosilyl group whose R < ¹² > is a methyl group are preferable, and a trifluorosilyl group is more preferable.

  The compound having a fluorosilyl group represented by the formula (7) is not particularly limited, and either a low molecular compound or a high molecular compound can be used. For example, inorganic silicon compounds; low molecular organic silicon compounds such as vinyl difluoromethoxysilane, vinyl trifluorosilane, phenyldifluoromethoxysilane, phenyltrifluorosilane; fluorinated poly having a fluorosilyl group represented by formula (7) at the terminal Examples thereof include polymer compounds such as siloxane, and preferred are fluorosilanes represented by the formula (6) and polymers having a fluorosilyl group represented by the formula (7) at the end of the main chain or side chain.

  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 single polymer in which the main chain skeleton is the same as a fluorosilyl group, that is, the number of fluorosilyl groups per molecule, the bonding position thereof, and the number of Fs that the fluorosilyl group has, and The polymer may be a single polymer having the same main chain skeleton, or may be a mixture of a plurality of polymers, any or all of which are different. Any of these fluorinated polymers can be suitably used as a resin component of a photocurable composition exhibiting rapid curability.

  As the main chain skeleton of the fluorinated polymer, specifically, the main chain skeleton of the (B) crosslinkable silicon group-containing polymer can be used, and since it is easy to handle and has good physical properties, polyoxypropylene, polyoxy Polyoxyalkylene polymers such as tetramethylene and polyoxyethylene-polyoxypropylene copolymers; (meth) acrylic acid ester copolymers are preferable, polyoxyalkylene polymerization is more preferable, and polyoxypropylene is the most preferable.

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

  The blending ratio of the silicon compound having a Si—F bond is not particularly limited, but is preferably 0.01 to 30 parts by mass with respect to 100 parts by mass in total of the component A and the (B) crosslinkable silicon group-containing polymer. 0.05 to 20 parts by mass is more preferable. When a polymer compound having a number average molecular weight of 3,000 or more, such as a fluorinated polymer, is used as the component (D), the amount is preferably 0.01 to 80 parts by mass with respect to 100 parts by mass in total of the component A and the component B. 0.01-30 mass parts is more preferable, and 0.05-20 mass parts is still more preferable. As a silicon compound having a Si—F bond, a low molecular compound having a fluorosilyl group having a number average molecular weight of less than 3,000 (for example, fluorosilanes represented by the formula (7) and fluorosilyl groups represented by the formula (6) Low molecular organic silicon compound, inorganic silicon compound having a fluorosilyl group, and the like) is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass in total of component A and component B, 0.05 -5 mass parts is more preferable.

(D component: fluorine compound)
Examples of the fluorine compound include one or more fluorine compounds selected from the group consisting of boron trifluoride, boron trifluoride complexes, fluorinating agents, and alkali metal salts of polyvalent fluoro compounds. A fluorine-type compound acts as a compound which accelerates | stimulates the hydrolytic condensation reaction of a crosslinkable silicon group.

  Examples of the boron trifluoride complex include boron trifluoride amine complex, alcohol complex, ether complex, and the like. Among the boron trifluoride complexes, amine complexes having both stability and catalytic activity are particularly preferred.

  Examples of the amine compound used for the boron trifluoride amine complex include monoethylamine and piperidine.

  Although there is no restriction | limiting in particular in the mixture ratio of a fluorine-type compound, 0.001-10 mass parts is preferable with respect to a total of 100 mass parts of A component and a crosslinkable silicon group containing organic polymer, 0.001-5 mass Part is more preferable, and 0.001 to 2 parts by mass is still more preferable. These fluorine compounds may be used alone or in combination of two or more.

  The photocurable composition can include one or more selected from the group consisting of a silicon compound having a Si—F bond and a fluorine-based compound. In particular, in the photocurable composition according to the present invention, when the effect as a photocurable composition to be post-cured (that is, converted into an adhesive) is improved, (B) the crosslinkable silicon group-containing polymer is a crosslinkable silicon. While containing a group containing organic polymer, it is preferable that a photocurable composition contains the silicon compound which has a Si-F bond.

(E component: tackifying resin)
The tackifying resin is not particularly limited. For example, a resin having a polar group such as a rosin ester resin, a phenol resin, a xylene resin, a xylene phenol resin, a terpene phenol resin, an aromatic or aliphatic having a relatively small polarity. -Various petroleum resins such as aromatic copolymer systems or alicyclic systems, or ordinary tackifying resins such as coumarone resins, low molecular weight polyethylene resins, terpene resins, and resins obtained by hydrogenation of these can be used. These may be used alone or in combination of two or more.

  Specific examples of these resins include α-methylstyrene single polymer resin [FTR Zero series, manufactured by Mitsui Chemicals, Inc.], styrene monomer single polymer resin [FTR 8000 series, Mitsui, as aromatic petroleum resin. Chemical Co., Ltd.], styrene monomer / aromatic monomer copolymer resin [FMR series, Mitsui Chemicals], α-methylstyrene / styrene copolymer resin [FTR 2000 series, Mitsui Chemicals, Inc. Aromatic styrene resins such as As aliphatic-aromatic copolymer petroleum resin, styrene monomer / aliphatic monomer copolymer resin [FTR 6000 series, manufactured by Mitsui Chemicals, Inc.], styrene monomer / α-methylstyrene / aliphatic monomer Examples thereof include aliphatic-aromatic copolymer styrene resins such as copolymer resins [FTR 7000 series, manufactured by Mitsui Chemicals, Inc.].

  (B) From the viewpoint of compatibility with the crosslinkable silicon group-containing polymer, the solubility parameter (hereinafter, abbreviated as “SP value” in principle) calculated by the Small method using Hoy's constant is 7.9 to 11. 0 is preferable, 8.2 to 9.8 is more preferable, and 8.5 to 9.5 is most preferable. From the viewpoint of the adhesive strength of the pressure-sensitive adhesive, it is preferable to select a resin having a polarity that matches the polarity of the adherend. When the tackifying resin is used for an adherend having a low polarity, it is preferable to use a tackifying resin having a low polarity. When the tackifying resin is used for an adherend having a high polarity, it is preferable to use a tackifying resin having a high polarity. When using a tackifier resin for a wide range of adherends from a high polarity adherend to a low polarity adherend, it is preferable to use a mixture of a low polarity tackifier resin and a high polarity tackifier resin. . The polarity (SP value) of the terpene phenol resin is as follows: Y series of Polyester (manufactured by Yasuhara Chemical Co., Ltd.) U series, SP value 8.69, T series SP value 8.81, S series SP value 8.98, G series Has an SP value of 9.07, and the K series has an SP value of 9.32. By selecting the polarity (SP value), it is possible to adapt to adherends of various polarities from adherends with low polarity to adherends with high polarity.

  The tackifier resin is preferably a terpene phenol resin or an aromatic petroleum resin from the viewpoint of good compatibility with the (B) crosslinkable silicon group-containing polymer. As the aromatic petroleum resin, an aromatic styrene resin and an aliphatic-aromatic copolymer styrene resin are preferable, and a terpene phenol resin and an aliphatic-aromatic copolymer styrene resin are more preferable. From the viewpoint of excellent adhesive strength, terpene phenol resin is most preferable. From the viewpoint of VOC, it is preferable to use an aliphatic-aromatic copolymer styrene resin.

  The blending ratio of the tackifying resin is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass with respect to 100 parts by mass in total of the component A and the (B) crosslinkable silicon group-containing polymer. From the viewpoint of exerting adhesive force, 5 parts by mass or more is preferable, and from the viewpoint of maintaining adequate hardness, exhibiting sufficient adhesive force, and ensuring good workability, 200 parts by mass or less is preferable.

(F component: polyfunctional monomer containing a photoradically polymerizable vinyl group, polyfunctional polymer containing a photoradically polymerizable vinyl group)
The photocurable composition can also contain a polyfunctional monomer from the viewpoint of ensuring the adhesiveness at high temperature. The more functional groups of the polyfunctional monomer, the greater the adhesive strength of the photocurable composition at high temperatures. Further, the functional group of the polyfunctional monomer is preferably bifunctional since the number of functional groups is a predetermined number or more, and the hardness when the photocurable composition is cured becomes a predetermined hardness or more. Furthermore, when the molecular weight of the polyfunctional monomer is a predetermined molecular weight or more, it contributes to maintaining the flexibility of the photocurable composition.

  As the polyfunctional monomer, for example, (F) a compound having a photoradically polymerizable vinyl group is used. As the compound (F) having a radical photopolymerizable vinyl group, various polyfunctional monomers having a radical photopolymerizable vinyl group can be used. For example, a compound having a (meth) acryloyl group and / or an N-vinyl compound in which a vinyl group is directly bonded to a nitrogen atom can be used.

  Moreover, it is preferable to contain polyfunctional (meth) acrylate as a crosslinking agent for the purpose of imparting heat resistance, cohesive force at high temperature, and the like to the photocurable composition. Examples of the polyfunctional (meth) acrylate include a polyfunctional (meth) acrylate monomer and an oligomer / polymer of polyfunctional (meth) acrylate (the oligomer and polymer may be collectively referred to as a polymer). Containing a polyfunctional polymer having a photo-radically polymerizable vinyl group as a polyfunctional (meth) acrylate polymer that can increase the distance between crosslinks in order to maintain the flexibility of the photocurable composition More preferably.

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

  As for the compounding quantity of a polyfunctional (meth) acrylate monomer, 0.01-5 weight part is preferable with respect to 100 weight part of A component, B component, and / or other monofunctional (meth) acrylate monomer. From the viewpoint of ensuring sufficient cohesive force under high temperature conditions, the amount of polyfunctional (meth) acrylate monomer is preferably 0.01 parts by weight or more, and from the viewpoint of ensuring good adhesive performance, 5 parts by weight. The following is preferable.

  As the polyfunctional (meth) acrylate polymer, polyether urethane (meth) acrylate (for example, “UV-3700B”, “UV-6100B” manufactured by Nihon Gosei Co., Ltd.), polyester urethane (meth) acrylate (for example, Japan) “UV-2000B”, “UV-3000B”, “UV-7000B”, “KHP-11”, “KHP-17” manufactured by Negami Kogyo Co., Ltd.), non-aromatic polycarbonate urethane (meth) acrylate (for example, , “Art Resin UN-9200A” manufactured by Negami Kogyo Co., Ltd.), acrylic (meth) acrylate (for example, “RC-300”, “RC-100”, “RC-200” manufactured by Kaneka Corporation), 1,2-polybutadiene Terminal urethane (meth) acrylate (for example, “TE-2000”, “TEA-1000” manufactured by Nippon Soda Co., Ltd.) 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 manufactured by Osaka Organic Chemical Co., Ltd.) -45 "), polyisoprene terminal (meth) acrylate, bisphenol A type epoxy (meth) acrylate, and the like.

  From the point of compatibility with the A component and the B component, polyether urethane (meth) acrylate, acrylic (meth) acrylate, polyester urethane (meth) acrylate, and non-aromatic polycarbonate urethane (meth) acrylate are preferable, Good compatibility with the A component and the B component, and from the viewpoint of ensuring flexibility of the cured product, polyether urethane (meth) acrylate and acrylic (meth) acrylate are more preferable, and polyether urethane (meth). Acrylate is more preferred.

  The polyfunctional (meth) acrylate polymer has a molecular weight of 500 to 50,000, and preferably 3,000 to 45,000, and 5,000 to 20 from the viewpoint of flexibility of the cured photocurable composition. 1,000 is more preferable. The glass transition temperature (Tg) is preferably 0 ° C. or lower from the viewpoint of maintaining and improving the adhesive performance when the photocurable composition exhibits adhesiveness.

  The blending amount of the polyfunctional (meth) acrylate polymer is preferably 3 to 30 parts by weight, more preferably 5 to 25 parts by weight with respect to 100 parts by weight of the component A, the component B and / or other monofunctional (meth) acrylate. Part. From the viewpoint of exhibiting sufficient cohesive force under high temperature conditions, the amount is preferably 3 parts by weight or more, and preferably 30 parts by weight or less from the viewpoint of ensuring good adhesive performance.

(Other additives)
In the photocurable composition according to the present invention, monofunctional (meth) acrylates, N-vinyl compounds, (meth), as necessary or within a range that does not inhibit the effect of the photocurable composition according to the present invention. Compound having acrylamide group, silane coupling agent, photo radical generator, photo sensitizer, extender, plasticizer, moisture absorbent, curing catalyst, physical property modifier for improving tensile properties, reinforcing agent, colorant, Various additives such as flame retardants, anti-sagging agents, antioxidants, anti-aging agents, ultraviolet absorbers, solvents, fragrances, pigments, dyes and fillers may be added.

Monofunctional (meth) acrylates are compounds having one (meth) acryloyloxy group, and both monomers (hereinafter also referred to as monomers) and polymers can be used. Monomers having a (meth) acryloyloxy group are preferred. Moreover, the polymer which has a (meth) acryloyloxy group from the point of the physical property of hardened | cured material is suitable. The monomer having one (meth) acryloyloxy group is not particularly limited as long as it is a compound having one (meth) acryloyloxy group. For example, a monofunctional (meth) acrylate monomer is mentioned. The (meth) acrylate group is preferably an acrylate group from the viewpoint of reactivity. Also, in that the adhesion of the photocurable composition according to the present invention is excellent, monofunctional (meth) acrylate monomer, T _g of homopolymer obtained from a monofunctional (meth) acrylate monomer is at 40 ° C. or less Preferably, it is preferably 10 ° C. or lower, and most preferably 0 ° C. or lower. In addition, it is preferable that B1 component is liquid from viewpoints, such as the ease of a mixing | blending.

As a monofunctional (meth) acrylate monomer, for example,
CH ₂ = CR ^α COO (C _m H _2m O) _n R ^β (8)
(In the general formula (8), R ^α is —H or —CH ₃ , m is an integer of 2 to 4, n is an integer of 1 to 20, R ^β is —H or an unsubstituted or substituted alkyl group, An unsubstituted or substituted phenyl group.). Specifically, as a monofunctional (meth) acrylate monomer, a compound in which ^Rβ is H in general formula (8), a (meth) acrylate having a hydroxyl group such as aliphatic epoxy (meth) acrylate; R in general formula (8) (meth) acrylate having an alkoxy group such as a compound in which ^β is an unsubstituted or substituted alkyl group; a compound in which R ^β is an unsubstituted or substituted phenyl group in the general formula (8), an aromatic such as an aryl (meth) acrylate (Meth) acrylate; long chain hydrocarbon type (meth) acrylate having 8 to 20 carbon atoms; alicyclic (meth) acrylate; (meth) acrylate having a heterocyclic group; (meth) acrylate having a carboximide group; Examples include (meth) acrylates having a crosslinkable silicon group. The compound of the long-chain hydrocarbon type (meth) acrylate having 8 to 20 carbon atoms and / or the compound of the general formula (8) is the point that the tackiness at the beginning of curing of the photocurable composition according to the present invention is excellent. Preferably, a long chain hydrocarbon (meth) acrylate having 8 to 20 carbon atoms, a (meth) acrylate having a hydroxyl group, and a (meth) acrylate having an alkoxy group are more preferable, and a long chain hydrocarbon having 8 to 20 carbon atoms. Most preferred are system (meth) acrylates.

  Specific examples of the monofunctional (meth) acrylate are as follows. First, 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. Examples of the (meth) acrylate having an alkoxy group include methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. Examples of the aromatic (meth) acrylate 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 availability, long-chain hydrocarbon (meth) acrylates having 8 to 18 carbon atoms are preferred. Examples of the alicyclic (meth) acrylate include cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate. 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.

  As the polymer having one (meth) acryloyloxy group, 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, a polyether (meth) acrylate polymer Examples thereof include an epoxy polymer and an epoxy (meth) acrylate polymer.

  Examples of the N-vinyl compound having a vinyl group include N-vinyl pyrrolidone and N-vinyl caprolactam. In the present invention, the N-vinyl compound is preferable from the viewpoint of reactivity and the difficulty of oxygen inhibition.

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

  The silane coupling agent acts as an adhesion promoter. Examples of the silane coupling agent include epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; γ-aminopropyltrimethoxysilane, N Amino group-containing silanes such as-(β-aminoethyl) -γ-aminopropyltrimethoxysilane; ketimines such as N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine Type silanes; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane; vinyl type unsaturated group-containing silanes such as vinyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane; γ-chloropropyltrimethoxysilane Chlorine atom-containing silanes such as γ-isocyanatopropyl Isocyanate-containing silanes such as triethoxysilane; alkyl silanes such as decyl trimethoxysilane; but phenyl-containing silanes such as phenyl trimethoxysilane, is not limited thereto. Also, modified amino group-containing silanes in which amino groups are modified by reacting amino group-containing silanes with epoxy group-containing compounds, isocyanate group-containing compounds, and (meth) acryloyl group-containing compounds containing the above silanes are used. May be.

  Amino group-containing silanes act as silanol condensation catalysts, and ketimine silanes produce amino group-containing silanes in the presence of moisture, which acts as silanol condensation catalysts. Therefore, it is preferable to use a silane coupling agent other than amino group-containing silanes and ketimine type silanes. In addition, when amino group-containing silanes or ketimine type silanes are used, they should be used while paying attention to the type and amount used within the range where the object and effect of the present invention are achieved.

  As described above, use of amino group-containing silanes and ketimine silanes may be limited in the present invention. However, when it is desirable to use amino group-containing silanes or ketimine type silanes as an adhesion-imparting agent, amino group-containing silanes are not generated by light irradiation without generating a compound having an amino group before light irradiation. Can be used (hereinafter also referred to as photoaminosilane-generating compound). Examples of the photoaminosilane generating compound include compounds in which the photofunctional group described in Document 1 is an o-nitrobenzyl group, a p-nitrobenzyl group, an oxime residue, a benzyl group, a benzoyl group, or a substituted group thereof. Can be mentioned. Examples of the photoaminosilane generating compound in which the photofunctional group is an o-nitrobenzyl group include 2-nitrobenzyl-N- [3- (trimethoxysilyl) propyl] carbamate, 2-nitrobenzyl-N- [3- (triethoxy Silyl) propyl] carbamate, 3,4-dimethoxy-2-nitrobenzyl-N- [3- (trimethoxysilyl) propyl] carbamate, and the like. Examples of the photoaminosilane-generating compound whose photofunctional group is a p-nitrobenzyl group include 4-nitrobenzyl-N- [3- (trimethoxysilyl) propyl] carbamate. Examples of the photoaminosilane-generating compound whose photofunctional group is a benzyl group include 1- (3,5-dimethoxyphenyl) -1-methylethyl-N- [3- (trimethoxysilyl) propyl] carbamate. Examples of the photoaminosilane-generating compound whose photofunctional group is an oxime residue group include benzophenone O-{[3- (trimethoxysilyl) propyl]} oxime.

  Although the compounding ratio of a silane coupling agent does not have a restriction | limiting in particular, 0.01-20 mass% is preferable in a photocurable composition, and 0.025-10 mass% is more preferable. These silane coupling agents may be used alone or in combination of two or more.

  The photo radical generator is a compound that generates radicals by irradiation with active energy rays such as ultraviolet rays and electron beams. The photo radical generator can also reinforce the effect of radicals generated from the photo base generator. Examples of the photoradical generator include benzoin ether derivatives, benzophenones, acetophenones, oxime ketones, acylphosphine oxides, titanocenes, thioxanthones, quinones, and derivatives obtained by increasing their molecular weight. .

  As the filler, a resin filler (resin fine powder) or an inorganic filler can be used. As the resin filler, a particulate filler made of an organic resin or the like can be used. For example, as the resin filler, organic fine particles such as polyethyl acrylate resin, polyurethane resin, polyethylene resin, polypropylene resin, urea resin, melamine resin, benzoguanamine resin, phenol resin, acrylic resin, and styrene resin can be used.

  The resin filler (resin fine powder) is preferably a true spherical filler that can be easily obtained by suspension polymerization of a monomer (for example, methyl methacrylate). Moreover, since a resin filler is suitably contained as a filler in the photocurable composition, a spherical crosslinked resin filler is preferable. In addition, when using the photocurable composition which manufactures the peripheral part etc. of a liquid crystal display device for the use as which light-shielding property is requested | required, it is preferable that a 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 curability can be obtained even when a single wavelength LED lamp or the like is used, and excellent light shielding properties and deep curability are obtained. Can be achieved.

  Examples of the inorganic filler extender include talc, clay, calcium carbonate, magnesium carbonate, anhydrous silicon, hydrated silicon, calcium silicate, titanium dioxide, and carbon black. These may be used alone or in combination of two or more.

  The photocurable composition of the present invention can further contain a diluent. By blending the diluent, the physical properties such as the viscosity of the photocurable composition can be adjusted. As the diluent, known diluents can be widely used, and are not particularly limited. For example, saturated hydrocarbon solvents such as normal paraffin and isoparaffin, HS dimer (trade name of Toyokuni Oil Co., Ltd.), etc. Examples of the solvent include α-olefin derivatives, aromatic hydrocarbon solvents, alcohol solvents such as diacetone alcohol, ester solvents, citrate solvents such as acetyltriethyl citrate, and ketone solvents.

  The flash point of the diluent is not particularly limited, but considering the safety of the photocurable composition, it is desirable that the flashpoint of the photocurable composition is high, and the volatile matter from the photocurable composition is low. Is preferred. Therefore, the flash point of the diluent is preferably 60 ° C. or higher, and more preferably 70 ° C. or higher. When mixing 2 or more types of diluents, it is preferable that the flash point of the mixed diluent is 70 degreeC or more. In general, since a diluent having a high flash point tends to have a low dilution effect on the photocurable composition, the flash point is preferably 250 ° C. or lower.

  In consideration of both safety and dilution effect of the photocurable composition, 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.

  The blending ratio of the diluent is not particularly limited, but it is preferable to blend 0 to 25% in the photocurable composition from the viewpoint of the balance between improvement in coating workability and decrease in physical properties due to blending. %, More preferably 1 to 7%. These diluents may be used alone or in combination of two or more.

  As the moisture absorbent, the silane coupling agent and silicate described above are suitable. The silicate is not particularly limited, and examples thereof include tetramethoxysilane, tetraalkoxysilane and the like, and partial hydrolysis condensates thereof.

  As other condensation reaction accelerating catalysts excluding component (C) and component (D), known curing catalysts can be widely used, and are not particularly limited. For example, organometallic compounds, amines, fatty acids, organic acids Examples thereof include phosphate ester compounds, and it is particularly preferable to use a silanol condensation catalyst. Examples of the silanol condensation catalyst include organic tin compounds; dialkyl tin oxides; reaction products of dibutyl tin oxide and phthalic acid esters; titanic acid esters; organoaluminum compounds; chelate compounds such as titanium tetraacetylacetonate; Organic acid bismuth etc. are mentioned. However, the toxicity of the resulting photocurable composition may increase depending on the amount of the organic tin compound added. Since the component (C) or component (D) of the present invention acts as a condensation reaction promoting catalyst, when using a curing catalyst other than these, it is preferable to use it within a range in which the object and effect of the present embodiment can be achieved. .

(Method for producing photocurable composition)
The method for producing the photocurable composition is not particularly limited. For example, a predetermined amount of the A component, the B component, the C component, and / or the D component is blended, and other blending substances are blended as necessary. It can be produced by degassing and stirring. The order of blending each component and other compounding substances is not particularly limited and can be determined as appropriate.

  The photocurable composition according to the present invention can be a one-component type or a two-component type as required, and can be suitably used particularly as a one-component type. The photocurable composition according to the present invention is a photocurable composition that exhibits tackiness by light irradiation and is post-cured, and can be cured at room temperature (for example, 23 ° C.). Although used suitably as a composition, you may accelerate | stimulate hardening suitably by heating as needed.

  The photocurable composition according to the present invention exhibits tackiness when irradiated with light, and is cured as an adhesive by a change over time. By this curing, a cured product of the photocurable composition can be obtained. The photocurable composition according to the present invention can be suitably used for electronic circuits, electronic parts, building materials, automobiles, and the like.

  Although there is no restriction | limiting in particular as conditions which irradiate light with respect to the photocurable composition which concerns on this invention, When irradiating an active energy ray at the time of hardening, as an active energy ray, rays, such as ultraviolet rays, visible rays, and infrared rays In addition to electromagnetic waves such as X-rays and γ-rays, electron beams, proton beams, neutron beams, and the like can be used. Curing by ultraviolet ray or electron beam irradiation is preferred, and curing by ultraviolet ray irradiation is more preferred from the viewpoint of curing speed, availability and price of the irradiation device, easiness of handling under sunlight or general illumination, and the like. The ultraviolet ray includes g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), and the like. The active energy ray source is not particularly limited, and includes, 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, and a metal halide depending on the properties of the photobase generator used. A light emitting diode is preferred.

As the irradiation energy, for example, in the case of ultraviolet rays, 10 to 20,000 mJ / cm ² is preferable, 20 to 10,000 mJ / cm ² is more preferable, and 50 to 5,000 mJ / cm ² is still more preferable. If it is less than 10 mJ / cm ² , the curability may be insufficient, and if it is greater than 20,000 mJ / cm ² , even if light is irradiated more than necessary, time and cost are wasted and the substrate is damaged. There is.

  Although there is no restriction | limiting in particular in the coating method to the to-be-adhered body of the photocurable composition based on this invention, Coating methods, such as screen printing, stencil printing, roll printing, dispenser coating, and spin coat, are used suitably.

  Moreover, there is no restriction | limiting in the time of application | coating to a to-be-adhered body of a photocurable composition, and light irradiation. For example, after irradiating light to a photocurable composition, it can join with a to-be-adhered body and a product can be manufactured. Moreover, a photocurable composition is apply | coated to a to-be-adhered body, a product can be manufactured by hardening a photocurable composition by irradiating light.

  For example, when bonding adherends together, the photocurable composition according to the present invention is applied to at least one adherend (application step). In the coating step, the photocurable composition may be applied to one adherend, or the photocurable composition may be applied to each of both adherends. From the viewpoint of simplifying the coating process, the photocurable composition can be applied to only one adherend. Next, light is irradiated to this photocurable composition (light irradiation process). The photocurable composition exhibits tackiness and adhesiveness by light irradiation. Subsequently, after light irradiation, the other adherend is bonded to one adherend by sandwiching the photocurable composition applied to one adherend between the other adherends (bonding). Process). Then, the other adherend is bonded to one adherend (bonding step). Thereby, a product in which adherends are bonded together is manufactured.

  The photocurable composition according to the present invention is a fast-curing photocurable composition excellent in workability, and is particularly useful as an adhesive / adhesive composition. That is, various cured composition-containing products can be produced using the photocurable composition according to the present invention. Specifically, the photocurable composition can be suitably used as an adhesive, a sealing material, an adhesive material, a coating material, a potting material, a paint, a putty material, a primer, and the like. In addition, the photocurable composition is, for example, a coating agent used for moisture-proof or insulation of a mounted circuit board, a coating agent used for coating a solar power generation panel or an outer peripheral portion of the panel, a sealing agent for multilayer glass, Sealing agents for vehicles, such as sealing agents for vehicles; Electrical and electronic parts materials such as solar cell back surface sealing agents; Electrical insulating materials such as insulating coating materials for electric wires and cables; Three-dimensional object formation by stereolithography Materials; adhesives; adhesives; elastic adhesives; contact adhesives and the like. Since the cured product obtained by curing the photocurable composition according to the present invention has flexibility, it can be applied to products that are bent or deformed or products that require flexibility.

(Effect of embodiment)
Since the photocurable composition according to the present invention is in a liquid state before light irradiation, it can be applied directly to an adherend and can be applied to an adherend having a complicated shape. And even if it does not interrupt | block from outside air, a photocurable composition exhibits adhesiveness rapidly by light irradiation. Therefore, according to the photocurable composition according to the present invention, after applying the photocurable composition to one adherend and irradiating with light, the other adherend is applied to the photocurable composition exhibiting adhesiveness. Can be pasted together. Then, the photocurable composition is post-cured due to a change with time. Thereby, the photocurable composition according to the present invention can easily bond a plurality of adherends to each other even when the adherend does not transmit light such as ultraviolet light.

  That is, the photocurable composition according to the present invention is not cured when not irradiated with active energy rays, and is cured by irradiation with active energy rays without being shielded from the outside air (that is, not covered with a film or the like). It is a curable composition, which is a photocurable composition having excellent rising adhesiveness after irradiation with active energy rays and fast curing with excellent adhesiveness. Therefore, a predetermined bonding time can be secured after light irradiation.

  Examples will be described in more detail below. Needless to say, these examples are illustrative and should not be interpreted in a limited manner.

(Synthesis Example 1) Synthesis of polyoxyalkylene polymer A1 having a trimethoxysilyl group at its terminal Polyoxypropylene was reacted with propylene oxide in the presence of zinc hexacyanocobaltate-glyme complex catalyst using ethylene glycol as an initiator. Diol was obtained. According to the method of Synthesis Example 2 of WO2015-088021, a polyoxyalkylene polymer having an allyl group at the end of the obtained polyoxypropylene diol was obtained. This polyoxyalkylene polymer having an allyl group at the end is reacted with trimethoxysilane, which is a silicon hydride compound, by adding a platinum vinyl siloxane complex isopropanol solution to react with the polyoxyalkylene having a trimethoxysilyl group at the end. A polymer A1 was obtained.

As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A1 having a trimethoxysilyl group 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 its terminal Polyoxypropylene was reacted with propylene oxide in the presence of a zinc hexacyanocobaltate-glyme complex catalyst using ethylene glycol as an initiator. Diol was obtained. According to the method of Synthesis Example 2 of WO2015-088021, a polyoxyalkylene polymer having an allyl group at the end of the obtained polyoxypropylene diol was obtained. This polyoxyalkylene polymer having an allyl group at the end is reacted with trimethoxysilane, which is a silicon hydride compound, by adding a platinum vinyl siloxane complex isopropanol solution to react with the polyoxyalkylene having a trimethoxysilyl group at the end. 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 In accordance with the method of Synthesis Example 4 of WO2015-088021, using 0.10 g of titanocene dicylide, 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 Hydroxyl value-converted molecular weight obtained by reacting propylene oxide in the presence of a zinc hexacyanocobaltate-glyme complex catalyst using polyoxypropylene diol having a molecular weight of about 2,000 as an initiator A polyoxypropylene diol having a molecular weight distribution of 1.3 was obtained. According to the method of Synthesis Example 2 of WO2015-088021, a polyoxyalkylene polymer having an allyl group at the end of the obtained polyoxypropylene diol was obtained. The polyoxyalkylene polymer having an allyl group at the terminal is reacted with methyldimethoxysilane, which is a silicon hydride compound, by adding a platinum vinylsiloxane complex isopropanol solution, and the polyoxyalkylene having a methyldimethoxysilyl group at the terminal is reacted. A polymer A4 was obtained. As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A4 having a methyldimethoxysilyl group by GPC, 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.

(Synthesis example 5) Synthesis | combination of the crosslinkable silicon group containing compound G1 which produces | generates an amino group by light 15.2-part 2-nitrobenzyl alcohol and 344 parts toluene were added to the flask, and it recirculate | refluxed at about 113 degreeC for 60 minutes. Thereafter, 20.5 parts of 3-isocyanatopropyltrimethoxysilane was added dropwise and stirred for 5 hours to produce a compound (a crosslinkable silicon group-containing compound that generates an amino group by light represented by the following formula (9) (hereinafter referred to as light). This was referred to as aminosilane-generating compound G1))). As a result of IR spectrum measurement of the photoaminosilane-generating compound G1, no —N═C═O bond was detected.

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 are used, and a polyoxy having a fluorosilyl group at the terminal is prepared in accordance with the method of Synthesis Example 4 of WO2015-088021. An alkylene polymer (hereinafter referred to as a fluorinated polymer) was obtained. ¹ H-NMR spectrum of the obtained fluorinated polymer (measured in a CDCl ₃ solvent using NMR 400 manufactured by Shimazu) was measured, and silylmethylene (—CH ₂ —Si) of polymer A4 as a raw material was measured. Peak (m, 0.63 ppm) disappeared, and a broad peak appeared on the low magnetic field side (0.7 ppm to).

Example 1
At the blending ratios shown in Table 1, each blended substance was added to a flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser, mixed and stirred to prepare a photocurable composition. Prepared.

In Table 1, the unit of the compounding amount of each compounding substance is “g”. The details of the compounding substances are as follows.
[Component A: Monoacrylate]
(2HPPA) monoacrylate; 2-hydroxy-3-phenoxypropyl acrylate (product name: PGA, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
[Component B: Liquid organic polymer]
(Polymer A1) Polyoxyalkylene polymer A1 synthesized in Synthesis Example 1
(Polymer A2) Polyoxyalkylene polymer A2 synthesized in Synthesis Example 2
(Polymer A3) (Meth) acrylic polymer A3 having a trimethoxysilyl group synthesized in Synthesis Example 3
[C component: photoinitiator]
(Irgacure 379) 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (product name: IIRGACURE 379EG, manufactured by BASF)
[Component D: Compound having Si-F bond]
(Fluorinated polymer) Fluorinated polymer synthesized in Synthesis Example 4 (BF ₃ -MEA) Boron trifluoride monoethylamine [E component: tackifying resin]
(YS Polystar T130) terpene phenol copolymer (SP value 8.81, softening point 130 ° C., product name: YS Polystar T130, manufactured by Yasuhara Chemical Co., Ltd.)
(YS Polystar K125) terpene phenol copolymer (SP value 9.32, softening point 125 ° C., product name: YS Polystar K125, manufactured by Yasuhara Chemical Co., Ltd.)
[F component: polyfunctional (meth) acrylate]
(UV3700B) Photoradical vinyl group-containing polyfunctional polymer (urethane acrylate, Mw: 38,000, Tg: -6 ° C, number of functional groups: 2, product name: UV3700B, manufactured by Nippon Synthetic Chemical Co., Ltd.)
[B1 component: monofunctional (meth) acrylate]
(PP-EO-A) o-phenylphenol EO-modified acrylate (Product name: ORD-01, manufactured by Nippon Shokubai Co., Ltd.)
(4HBA) 4-hydroxybutyl acrylate (Product name: 4HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
(LA) Lauryl acrylate (Product name: Light Ester LA, manufactured by Kyoeisha Chemical Co., Ltd.)
(ECA) Ethyl carbitol acrylate (Product name: Biscoat # 190, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
(KBM5103) 3- (Trimethoxysilyl) propyl acrylate (Product name: KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
[Photoaminosilane] Photoaminosilane-generating compound G1 synthesized in Synthesis Example 5

(Peel adhesion strength test)
The photocurable composition according to Example 1 was applied to the first adherend (PET film) using a glass rod. The thickness of the photocurable composition is 200 μm. Next, the photocurable composition on the first adherend was irradiated with ultraviolet rays (UV) [irradiation conditions: UV-LED lamp (wavelength 365 nm, illuminance: 1000 mW / cm ² ), integrated light quantity: 3000 mJ / cm ² ]. Immediately after the UV irradiation, the first adherent (aluminum adherend subjected to sulfuric acid alumite treatment) with an area of 25 mm × 80 mm is sandwiched between the UV-irradiated photocurable composition. Bonding was performed on the adherend, and pressure was applied using a 2 kg roller. After applying pressure, the peel strength was measured immediately at a test speed of 300 mm / min in accordance with JIS K6854-2 (adhesive-peeling peel strength test method Part 2: 180 degree peel method). The test results are shown in the column of “Peel Test 1” in Table 1.

  Further, in the same manner as described above, immediately after UV irradiation, the second adherend is bonded to the first adherend so as to sandwich the UV-cured photocurable composition, and is pressed using a 2 kg roller. A sample was also prepared that was clamped and cured for 7 days at 23 ° C. and 50% RH. The peel strength of the sample was measured in the same manner as described above. The test results are shown in the column of “Peel Test 2” in Table 1. In Table 1, the unit of peel adhesion strength is “N / 25 mm”.

(Shear bond strength test)
The photocurable composition according to Example 1 was applied to the first adherend (aluminum adherend subjected to the sulfate alumite treatment) using a glass rod. The thickness of the photocurable composition is 200 μm. Next, the photocurable composition on the first adherend was irradiated with ultraviolet rays (UV) [irradiation conditions: UV-LED lamp (wavelength 365 nm, illuminance: 1000 mW / cm ² ), integrated light quantity: 3000 mJ / cm ² ]. Immediately after the UV irradiation, the first adherent (aluminum adherend subjected to sulfuric acid alumite treatment) is sandwiched between the UV-irradiated photocurable composition with an area of 25 mm × 25 mm. Affixed to the adherend, pressure was applied using a small eyeball clip. After the pressure was applied, the tensile shear bond strength was measured at a test speed of 50 mm / min in accordance with the JIS K6850 rigid adherend tensile shear bond strength test method. The test results are shown in the column of “Shear test 1” in Table 1.

Further, in the same manner as described above, immediately after UV irradiation, the second adherend is bonded to the first adherend so as to sandwich the photocurable composition irradiated with UV in an area of 25 mm × 25 mm. A sample was also prepared by applying pressure using a small eyeball clip and curing for 7 days at 23 ° C. and 50% RH. And also about the said sample, it carried out similarly to the above, and measured the tensile shear bond strength. The test results are shown in the column of “Shear test 2” in Table 1. In Table 1, the unit of tensile shear bond strength is “N / mm ² ”.

In the peel test and the shear test of Table 1, the results determined according to the following criteria are indicated by predetermined symbols.
“Peel test 1 (immediately after irradiation)”: “◎” is indicated when the peel adhesive strength is 5 N / 25 mm or more, “◯” is indicated when it is 1 N / 25 mm or more, and “X” is indicated when it is less than 1 N / 25 mm.
“Peeling test 2 (curing 7 days)”: “◎” when the peel adhesion strength is 10 N / 25 mm or more, “◯” when 3 N / 25 mm or more, and “X” when less than 3 N / 25 mm .
"Shear test 1 (immediately after irradiation)": tensile case shear bond strength of 0.4N / mm ² or more "◎", a 0.2N / mm ² or more when the "○", 0.2N / mm ² If it is less than "x", it is marked.
"Shear Test 2 (curing 7 days)": Tensile case shear strength of 1N / mm ² or more "◎", 0.5 N / mm ² or more when the "○", less than 0.5 N / mm ² In the case of “×”, “×” is marked.

(Examples 2-9 and Comparative Examples 1-4)
As shown in Table 1, after obtaining a photocurable composition by the same method as Example 1 except having changed the compounding substance, the characteristic of the obtained photocurable composition was evaluated similarly to Example 1. did. The results are shown in Table 1. Note that the measurement value of “0” in the evaluation of Comparative Example 4 (peeling tests 1 and 2 and shearing tests 1 and 2) is insufficiently cured on the surface (that is, slightly muted when touched with a finger). Present) is not sticky and adhesive.

  As shown in Table 1, it was shown that all the photocurable compositions according to the examples exhibited excellent tackiness immediately after UV irradiation, and exhibited superior adhesiveness due to changes over time.

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

Claims (8)

(A) a monoacrylate represented by the following general formula (1) and suppressing oxygen inhibition;
(B) a crosslinkable silicon group-containing polymer;
(C) A photocurable composition containing a photoinitiator.
(In General Formula (1), R ¹ represents —H or —CH ₃ , and R ^{2 to} R ⁶ each independently represent a hydrogen atom, or a nitro group, a cyano group, a hydroxy group, a halogen atom, an acetyl group, A carbonyl group, a substituted or unsubstituted allyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, a heterocyclic structure-containing group, and a plurality A substituent containing at least one group selected from the group consisting of a group having a ring of at least two groups selected from the group consisting of R ^{2 to} R ⁶ are bonded to each other, And may form a cyclic structure together with the carbon atoms.)   The photocurable composition according to claim 1, further comprising (D) a compound having a Si-F bond and at least one compound selected from the group consisting of boron trifluoride.   (E) The photocurable composition of Claim 1 or 2 which further contains tackifying resin.   (F) The photocurable composition of any one of Claims 1-3 which further contains polyfunctional (meth) acrylate.   The photocurable composition according to claim 4, wherein the (F) polyfunctional (meth) acrylate is a polyfunctional polymer containing a photoradically polymerizable vinyl group.   The hardening composition containing product comprised using the photocurable composition of any one of Claims 1-5. A laminating method for laminating a plurality of adherends,
An application step of applying the photocurable composition according to any one of claims 1 to 5 to at least one adherend;
A light irradiation step of irradiating the photocurable composition applied to the one adherend with light;
A bonding method comprising: a bonding step in which the photocurable composition applied to the one adherend and irradiated with the light is sandwiched between the other adherends. A method for producing a product having a plurality of adherends,
An application step of applying the photocurable composition according to any one of claims 1 to 5 to at least one adherend;
A light irradiation step of irradiating the photocurable composition applied to the one adherend with light;
A method of manufacturing a product, comprising: an adhesion step in which the photocurable composition applied to the one adherend and irradiated with the light is sandwiched between the other adherends and adhered.