WO2017098972A1

WO2017098972A1 - Bonding method using photocurable adhesive

Info

Publication number: WO2017098972A1
Application number: PCT/JP2016/085485
Authority: WO
Inventors: 翔馬河野; 尚孝河村; 智洋緑川; 岡村　直実; 宏士山家
Original assignee: セメダイン株式会社
Priority date: 2015-12-08
Filing date: 2016-11-30
Publication date: 2017-06-15
Also published as: KR20180090818A; JP6156607B1; CN108431157B; JPWO2017098972A1; CN108431157A

Abstract

Provided are: a photocurable adhesive which is able to be applied to objects to be bonded having various shapes, while having excellent surface curability and quickly exhibiting adhesiveness after light irradiation; a product which contains this adhesive; a bonding method; and a method for producing this product. This photocurable adhesive contains: (A) a monoacrylate which is represented by general formula (1) and suppresses oxygen inhibition; an organic compound which is selected from the group consisting of (B1) monofunctional (meth)acrylates and (B2) liquid organic polymers; and (C) a photoinitiator. (In general formula (1), R¹ represents a hydrogen atom or a methyl group; and each of R² to R⁶ independently represents a hydrogen atom or a substituent.)

Description

Adhesion method using photocurable adhesive

The present invention relates to an adhesion method using a photocurable pressure-sensitive adhesive that can be photocured quickly even in air.

In Patent Document 1, a photocurable composition containing a photopolymerizable acrylic ester is applied to one adherend, and then irradiated with ultraviolet rays to polymerize the acrylic ester to increase the viscosity (B-stage formation). It is said that the adhesiveness is imparted), and a method for bonding and fixing the other adherend in this state is disclosed. As a specific example, the manufacture of a radio frequency identification (RFID) tag using an antenna component as one adherend and an IC chip as the other adherend is shown. In Patent Document 1, moisture curable resin is further used for the photocurable composition to ensure adhesion.

Thus, after applying the photocurable composition containing a photopolymerizable acrylic ester to one adherend and polymerizing the acrylic ester by light irradiation to impart tackiness, the other adherend The method of adhering bodies is thought to be particularly useful in the manufacture of electronic equipment. This is because it is easy to peel off the adherend once bonded for alignment or the like according to such a method. In addition, although the same method is possible using an adhesive sheet or an adhesive tape, it is often difficult to place the adhesive sheet or adhesive tape in a predetermined shape and place it in a predetermined place, This is because, according to the bonding method, it is relatively easy to apply the uncured photocurable composition to a predetermined place.

However, although acrylic acid esters have photopolymerizability, it is known that polymerization is inhibited in the presence of oxygen such as in the air, and polymerization does not proceed or irradiation for a long time is necessary. And it was necessary to irradiate with strong light. Actually, in Example 1 of Patent Document 1, phenoxyethyl acrylate is used as an acrylic ester, but it takes a time of 1 hour or less for photopolymerization. In the manufacture of electronic equipment, it is considered that the time for photopolymerization is preferably in units of seconds from the viewpoint of productivity. In order to solve the problem of oxygen inhibition, it is possible to irradiate with light in a nitrogen atmosphere or to irradiate with light using a transparent cover film, but separate equipment is required.

JP-T 2009-530441 International Publication WO2013-161812

A problem to be solved by the present invention is an adhesion method in which a plurality of adherends are bonded using a photocurable pressure-sensitive adhesive containing an acrylate ester, and the photopolymerization of the acrylate ester is rapidly performed even in the presence of oxygen. It is an object of the present invention to provide an adhesion method that is advanced and does not require long-time light irradiation or oxygen shielding equipment.

The present inventors have found that when an acrylic ester having a hydroxyl group disclosed in Patent Document 2 is used as an acrylic ester, the photopolymerization of the acrylic ester proceeds rapidly even in the presence of oxygen, leading to the present invention. . In Patent Document 2, for example, as described in Examples in paragraph [0071] of Patent Document 2, an ultraviolet curable pressure-sensitive adhesive composition is applied onto a release-treated polyester film and pre-cured by UV irradiation. Then, the cured product coated surface and the release-treated polyester film are bonded together to block air, and cured by being irradiated with UV to obtain an adhesive layer. That is, the pre-curing increases the viscosity of the inside of the composition, not the surface, and in that state, the air is shut off by being bonded to the release-treated polyester film, and the curing is advanced by irradiating light again to form the adhesive layer. It has gained. Therefore, Patent Document 2 does not describe or suggest the viewpoint of oxygen inhibition required for the pressure-sensitive adhesive composition in the field construction that requires work in air without using release paper. Therefore, the object of the present invention cannot be achieved. That is, the present invention is the following bonding method.

The present invention is a method of bonding a plurality of adherends, wherein (A) a monoacrylate represented by the following general formula (1), (B1) a monofunctional (meth) acrylate, and (B2) a liquid organic material A coating step of applying a photocurable pressure-sensitive adhesive that exhibits adhesiveness by light irradiation containing at least one organic compound selected from the group consisting of polymers and (C) a photoinitiator to at least one adherend. A light irradiation step of irradiating light to the photocurable adhesive applied to one adherend, and the other application to the photocurable adhesive applied to one adherend and irradiated with light. And a step of adhering a body (excluding the adhesive sheet protective sheet as the other adherend).

In general formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ^{2 to} R ⁶ are each independently a hydrogen atom or a substituent.

In the above bonding method, the photocurable pressure-sensitive adhesive may further contain (D) a tackifying resin.

In the above bonding method, the photocurable pressure-sensitive adhesive may further contain (E) a compound containing two or more photoradically polymerizable vinyl groups.

In the above bonding method, (E) the compound containing two or more photoradically polymerizable vinyl groups may be a polymer.

In the above bonding method, the liquid organic polymer (B2) may be a polymer having a crosslinkable silicon group.

Moreover, in order to achieve the above object, the present invention provides an adhesive body manufactured using the bonding method described in any one of the above.

In order to achieve the above object, the present invention is a photocurable pressure-sensitive adhesive that exhibits adhesiveness by light irradiation, and comprises (A) a monoacrylate represented by the general formula (1) and (B1) monofunctional There is provided a photocurable pressure-sensitive adhesive for on-site construction containing at least one organic compound selected from the group consisting of (meth) acrylate and (B2) liquid organic polymer, and (C) a photoinitiator.

In Patent Document 2, an ultraviolet curable pressure-sensitive adhesive composition containing a predetermined polyfunctional urethane (meth) acrylate oligomer, a tackifier, a monofunctional epoxy ester (meth) acrylate, and a photopolymerization initiator is disclosed. However, unlike the present invention, the ultraviolet curable pressure-sensitive adhesive composition according to Patent Document 2 is not used for on-site construction, but is used for a purpose different from the present invention.

The bonding method according to the present invention is a bonding method in which a plurality of adherends are bonded using a photocurable pressure-sensitive adhesive containing an acrylate ester, and the photopolymerization of the acrylate ester is rapid even in the presence of oxygen. Therefore, it is possible to provide an adhesion method that does not require long-time light irradiation or oxygen shielding equipment.

It is a schematic diagram of the printed circuit board used for the LED chip bonding test, and the LED chip. It is a schematic diagram of the process of bonding an LED chip on a printed circuit board.

The adhesion method of the present invention is not a method for producing a pressure-sensitive adhesive product such as a pressure-sensitive adhesive sheet or a pressure-sensitive adhesive tape, but directly applies a raw material that becomes a pressure-sensitive adhesive by light irradiation to the adherend, thereby generating a pressure-sensitive adhesive on the adherend, This is a method of adhering the other adherend to this. That is, in the bonding method of the present invention, the photocurable pressure-sensitive adhesive is not used after being formed into a shape such as a tape, but is directly applied to one adherend and directly adhered to the other adherend. (In other words, the other adherend is not a film such as a release liner, but an adherend that is actually bonded to one adherend).

And as an application of the bonding method of the present invention, it can be used for bonding electronic / electrical parts and the like, and is particularly suitable for bonding electronic parts. Here, “for on-site construction” in the present invention means that a photocurable adhesive is used as it is for bonding at a site where an electronic component or the like is manufactured. That is, in the present invention, the pressure-sensitive adhesive is processed into a shape such as a tape to produce a molded body, and the molded body is not used in a place different from the processing place, but the photocurable pressure-sensitive adhesive of the present invention is used on one side. It refers to an application in which an adherend is directly applied to the adherend and one adherend is attached to the other adherend in that state (or at the site).

Further, the photocurable pressure-sensitive adhesive of the present invention is a photocurable pressure-sensitive adhesive that quickly exhibits adhesiveness upon irradiation with light such as active energy rays. That is, the photocurable pressure-sensitive adhesive comprises (A) a compound that exhibits cohesive force and suppresses oxygen inhibition by oxygen in the environment, (B) a compound that exhibits flexibility, and (C) radicals by light irradiation. And a compound that generates Specifically, the photocurable pressure-sensitive adhesive of the present invention comprises (A) a monoacrylate represented by the following general formula (1), (B1) monofunctional (meth) acrylate as the B component, and B component. (B2) contains at least one organic compound selected from the group consisting of liquid organic polymers, and (C) a photoinitiator. Moreover, a photocurable adhesive may further contain (D) tackifying resin. Further, the photocurable pressure-sensitive adhesive may further contain (E) a polyfunctional monomer containing a photoradically polymerizable vinyl group and / or (E) a polyfunctional polymer containing a photoradically polymerizable vinyl group. it can.

In general formula (1), in general formula (1), R ¹ represents a hydrogen atom (—H) or a methyl group (—CH ₃ ), and R ^{2 to} R ⁶ each independently represents a hydrogen atom or a substituent. It is. 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, 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 pressure-sensitive adhesive 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 photocurable pressure-sensitive adhesives using various compounds, the photocuring according to the present invention The A component of the adhesive was found to be 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.

Here, monoacrylates having a hydroxyl group other than the monoacrylate represented by the general formula (1) (for example, 4-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, etc.) cannot provide the effects of the present invention.

In addition, the viewpoint which makes the hardened | cured material more flexible than the hardened | cured material obtained from epoxy acrylate, acrylamide, etc. from the adhesive obtained from photocurable adhesive, and the postcure of an adhesive, and / or an epoxy From the viewpoint of using a compound having a glass transition temperature relatively lower than the glass transition temperature, such as acrylate or acrylamide, the component A is preferably not monofunctional but monoacrylate.

Here, as the mechanism for suppressing the polymerization inhibition by oxygen, the following mechanism is presumed. 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 pressure-sensitive adhesive is easy to be post-cured (adhesive) due to a change with time after showing the tackiness by light irradiation. 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 trialkoxysilyl group [—Si (OR) ₃ ] such as trimethoxysilyl group and dialkoxysilyl group [—Si (CH ₃ ) (OR) such as methyldimethoxysilyl group. ₂ ], and 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.

(B1 component: monofunctional (meth) acrylate)
The B1 component is a compound that causes the photocurable pressure-sensitive adhesive to exhibit flexibility. The monofunctional (meth) acrylate is a compound having one (meth) acryloyloxy group, and any of a monomer (hereinafter also referred to as a monomer) and a polymer can be used. ) Monomers having an 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 pressure-sensitive adhesive is excellent, monofunctional (meth) acrylate monomer is preferably the T _g of the homopolymer obtained from a monofunctional (meth) acrylate monomer is 40 ° C. or less 10 ° C. or lower is more preferable, and 0 ° C. or lower is most preferable. 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 (2)
(In the general formula (2), 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 (2), a (meth) acrylate having a hydroxyl group such as aliphatic epoxy (meth) acrylate; R in general formula (2) (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 (2), 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. From the viewpoint of excellent adhesiveness of the photocurable adhesive, a long-chain hydrocarbon (meth) acrylate having 8 to 20 carbon atoms and / or a compound of the general formula (2) is preferable, and the carbon number is 8 to 20 20 long-chain hydrocarbon (meth) acrylates, (meth) acrylates having a hydroxyl group, (meth) acrylates having an alkoxy group are more preferred, and long-chain hydrocarbon (meth) acrylates having 8 to 20 carbon atoms are the most. preferable.

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. Further, N- (meth) acryloyloxyethyl hexahydrophthalimide and the like can be mentioned. Examples of the (meth) acrylate having a crosslinkable silicon group include 3- (trimethoxysilyl) propyl (meth) acrylate.

Further, 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.

(B2 component: Liquid organic polymer)
Specific examples of the main chain skeleton of the liquid organic polymer include polyoxyalkylene polymers such as polyoxypropylene, polyoxytetramethylene and polyoxyethylene-polyoxypropylene copolymers; ethylene-propylene copolymers. Polymers, polyisobutylene, polyisoprene, polybutadiene, hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; condensation of dibasic acids such as adipic acid and glycols, Or polyester polymer obtained by 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; Acrylic acid ester monomers, vinyl acetate, acrylonitrile, styrene, etc. Vinyl polymer obtained by radical polymerization of monomer; Graft polymer obtained by polymerizing vinyl monomer in organic polymer; Polysulfide polymer; Polyamide polymer; Polycarbonate polymer; Diallyl phthalate heavy Examples include coalescence. Two or more kinds of these skeletons may be included 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. A photocurable pressure-sensitive adhesive is preferred because of its excellent 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.

The liquid organic polymer may be linear or branched, and its number average molecular weight is about 500 to 100,000, more preferably 1,000 to 50,000, particularly preferably in terms of polystyrene in GPC. Is 3,000 to 30,000. If the number average molecular weight is less than 500, there is an inconvenient tendency in terms of elongation characteristics of the photocurable pressure-sensitive adhesive, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity.

(Polyoxyalkylene polymer)
The polyoxyalkylene polymer is a polymer having a repeating unit represented by the general formula (3).
-R ⁷ -O- (3)
In the general formula (3), R ⁷ 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 method for synthesizing a polyoxyalkylene polymer include, but are not limited to, a polymerization method using an alkali catalyst such as KOH, for example, a polymerization method using a double metal cyanide complex catalyst, and the like. According to the polymerization method using a double metal cyanide complex catalyst, 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.

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

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.

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

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

These may be used alone or may be copolymerized. Furthermore, the number of 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 method for producing the (meth) acrylate polymer is not particularly limited, and for example, a radical polymerization method using a radical polymerization reaction can be used. 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, in order to obtain a (meth) acrylate polymer having a narrow molecular weight distribution and low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high rate It is preferable to use a controlled radical polymerization method.

Examples of the controlled radical polymerization method include free radical polymerization method and living radical polymerization method using a chain transfer agent having a specific functional group, such as an addition-cleavage transfer reaction (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 liquid organic polymers may be used alone or in combination of two or more. Specifically, an organic polymer obtained by blending two or more selected from the group consisting of a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth) acrylate polymer can also be used. .

Various methods are mentioned as a manufacturing method of the organic polymer which blended the polyoxyalkylene type polymer and the (meth) acrylic acid ester type polymer. For example, the molecular chain substantially has the general formula (4):
—CH ₂ —C (R ⁸ ) (COOR ⁹ ) — (4)
(Wherein R ⁸ represents a hydrogen atom or a methyl group, R ⁹ represents an alkyl group having 1 to 5 carbon atoms) and a general formula (5):
—CH ₂ —C (R ⁸ ) (COOR ¹⁰ ) — (5)
(Wherein R ⁸ is the same as described above, and R ¹⁰ represents an alkyl group having 6 or more carbon atoms) A copolymer composed of a (meth) acrylic acid ester monomer unit is represented by a polyoxyalkylene type The method of blending and producing a polymer is mentioned.

As R ^{9 in the} general formula (4), for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group and the like have 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms, An alkyl group having 1 to 2 carbon atoms is preferable. The alkyl group of R ⁹ may alone, or may be a mixture of two or more.

R ^{10 in the} general formula (5) is, for example, a long group having 6 or more carbon atoms such as 2-ethylhexyl group, lauryl group or stearyl group, usually 7 to 30 carbon atoms, preferably 8 to 20 carbon atoms. Chain alkyl groups. The alkyl group of R ¹⁰ is same as in the case of R ^9, may be alone or in admixture.

The molecular chain of the (meth) acrylic acid ester copolymer is substantially composed 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 by 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 is improved. The (meth) acrylic acid ester polymer may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the compounding ratio of a polyoxyalkylene polymer and a (meth) acrylic acid ester polymer, A total of 100 mass parts of a (meth) acrylic acid ester polymer and a polyoxyalkylene polymer. The (meth) acrylic acid ester polymer is preferably in the range of 10 to 60 parts by mass, more preferably in the range of 20 to 50 parts by mass, and still more preferably 25 to 45 parts by mass. Is within the range. When the amount of the (meth) acrylic acid ester polymer is more than 60 parts by mass, the viscosity becomes high and workability deteriorates, which is not preferable.

Furthermore, as a method for producing an organic polymer obtained by blending a (meth) acrylic acid ester copolymer, a (meth) acrylic acid ester monomer is polymerized in the presence of the organic polymer. You can use the method to do.

When blending two or more kinds of polymers, the saturated hydrocarbon polymer and / or the (meth) acrylic acid ester polymer is 10 to 200 masses per 100 mass parts of the polyoxyalkylene polymer. It is preferable to use parts, more preferably 20 to 80 parts by weight.

In addition, when two or more organic polymers are used, even when a solid organic polymer is included, when a solid organic polymer is mixed with another organic polymer, it becomes liquid (that is, Any organic polymer in which a solid organic polymer is dissolved in another organic polymer and becomes liquid can be used as the B2 component according to the present invention. Further, the liquid organic polymer preferably exhibits a liquid state at 20 ° C., more preferably exhibits a liquid state at 0 ° C., and more preferably at −10 ° C. from the viewpoint of ensuring ease of handling when blended with other components. More preferably, it shows a liquid state.

In addition, when a liquid organic polymer containing a crosslinkable silicon group is used as the liquid organic polymer, the photocurable pressure-sensitive adhesive exhibits adhesiveness by light irradiation and is then post-cured (adhesive) due to change over time. It becomes easy to do. The liquid organic polymer becomes a liquid organic polymer containing a crosslinkable silicon group by introducing a crosslinkable silicon group.

(Liquid organic polymer containing a crosslinkable silicon group)
As the crosslinkable silicon group of the liquid organic polymer containing a crosslinkable silicon group, for example, a group represented by the general formula (6) is suitable.

In formula (6), R ^γ represents an organic group. R ^γ is preferably a hydrocarbon group having 1 to 20 carbon atoms. Among these, R ^γ is particularly preferably a methyl group. R ^γ may have a substituent. When two or more R ^γ are present, the plurality of R ^γ 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 pressure-sensitive adhesive having a sufficient curing rate in consideration of curability, a in formula (6) 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. Examples thereof include a silyl group [—SiR ¹ (OR) ₂ ], a trialkoxysilyl group [—Si (OR) ₃ ] is preferable in terms of high reactivity, and a trimethoxysilyl group is more preferable. Here, R is an alkyl group such as a methyl group or an ethyl group.

Moreover, the crosslinkable silicon group may be used alone or in combination of two or more. The crosslinkable silicon group can be present in the main chain, the side chain, or both.

The blending ratio of the monofunctional (meth) acrylate and the liquid organic polymer is 100 parts by weight of the A component and the B1 component and / or the B2 component (when both the B1 component and the B2 component are used, the A component and the B1 component 10 to 80 parts by mass, more preferably 20 to 70 parts by mass, most preferably 30 to 60 parts by mass with respect to 100 parts by mass in total with the B2 component (hereinafter also referred to as 100 parts by mass of liquid AB component)) . From the viewpoint of maintaining the hardness of the cured product appropriately and exhibiting sufficient adhesive strength, the blending ratio of the monofunctional (meth) acrylate and the liquid organic polymer is preferably 10 parts by mass or more, and oxygen inhibition by the A component is suppressed. From the viewpoint of exerting a suppressing effect and exhibiting sufficient adhesive strength, the blending ratio of the monofunctional (meth) acrylate and the liquid organic 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 liquid organic polymer (B2) when irradiated with light. In particular, when the organic polymer contains a crosslinkable silicon group, it is highly effective. 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. The radical generated from the photobase generator has a function of curing the component A, and the base generated from the photobase generator has a function of curing the liquid organic polymer containing a crosslinkable silicon group.

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. In addition, among the non-cyclic amidine compounds, for example, the photo-base generator that generates the aryl-substituted guanidine-based compound or the aryl-substituted biguanide-based compound described in Document 1 is used as a catalyst for the liquid organic polymer (B2). It is preferable because it shows a tendency to improve the curability of the surface, and a tendency to improve the adhesiveness 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 known because it is easily available industrially, and has a pKa value of 12 or more for the conjugate acid and exhibits high catalytic activity. -7 (DBU) and 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) are particularly preferred.

As the photobase generator, various photobase generators can be used. 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 the photolatent primary amine and the photolatent secondary amine include orthonitrobenzyl urethane compounds described in Document 1, dimethoxybenzyl urethane compounds, benzoins carbamates, o-acyloximes, o- Carbamoyl oximes; N-hydroxyimide carbamates; formanilide derivatives; aromatic sulfonamides; cobalt amine complexes and the like.

Examples of photolatent tertiary amines include α-aminoketone derivatives, α-ammonium ketone derivatives, benzylamine derivatives, benzylammonium salt derivatives, α-aminoalkene derivatives, α-ammonium alkene derivatives, 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, 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 And α-aminoketone compounds that generate tertiary amines having a group.

Examples of 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 the benzylamine derivative include 5-benzyl-1,5-diazabicyclo [4.3.0] nonane, 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.

Examples of the benzylammonium salt derivative 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 the photobase generators, photolatent tertiary amines are preferable from the viewpoint that the generated bases exhibit high catalytic activity, because the base generation efficiency is high and the storage stability as a photocurable adhesive is good. , Benzylammonium salt derivatives, benzyl-substituted amine derivatives, α-aminoketone derivatives, α-ammonium ketone derivatives are preferred. In particular, α-aminoketone derivatives and α-ammonium ketone derivatives are more preferable due to better base generation efficiency, and α-aminoketone derivatives are 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-aminoketone 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 weight, more preferably 0.1 to 40 parts by weight, and 0.5 to 30 parts by weight with respect to 100 parts by weight of the liquid AB component. Part is more preferred.

The photocurable pressure-sensitive adhesive is used in combination with a photoinitiator (particularly, a base generated from a photobase generator) within a range that does not inhibit the function and curing of the photocurable pressure-sensitive adhesive. You may contain the catalyst action promoter which improves the cure rate of an adhesive. Examples of the catalyst accelerator include silicon compounds having a Si—F bond, fluorine compounds, and the like.

(Silicon compound having Si-F bond)
As the silicon compound having a Si—F bond, various compounds containing a silicon group having a Si—F bond (hereinafter sometimes referred to as a fluorosilyl group) can be used. As the silicon compound having a Si—F bond, any of an inorganic compound and an organic compound can be used, and there is no particular limitation, and any of a low molecular compound and a high molecular compound can be used. As the silicon compound having a Si—F bond, 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 adhesive becomes low viscosity is preferable.

Specific examples of the silicon compound having a Si—F bond include fluorosilanes described in Document 1 represented by Formula (7), compounds having a fluorosilyl group described in Document 1 represented by Formula (8) ( Preferred examples include fluorinated compounds) and organic polymers having a fluorosilyl group described in Document 1 (hereinafter also referred to as fluorinated polymers).

R ¹¹ _4-d SiF _d (7)
(In Formula (7), R ¹¹ is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ¹² SiO— (R ¹² 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 ¹¹ And when there are a plurality of R ^{12 s} , they may be the same or different.)

-SiF _d R ¹¹ _e Z _f (8)
(In Formula (8), R ¹¹ and d are the same as those in Formula (7), Z is each independently a hydroxyl group or other hydrolyzable group excluding fluorine, and e is any one of 0 to 2) F is any one of 0 to 2, and d + e + f is 3. When a plurality of R ¹¹ , R ¹² and Z are present, they may be the same or different.

Examples of the fluorosilanes represented by the formula (7) include fluorosilanes represented by the formula (7). Examples thereof include fluorodimethylphenylsilane, vinyl trifluorosilane, γ-methacryloxypropyl trifluorosilane, octadecyl trifluorosilane, and the like.

In the compound having a fluorosilyl group represented by the formula (8), the hydrolyzable group represented by Z is preferably an alkoxy group from the viewpoint of mild hydrolyzability and easy handling, and R ¹¹ is a methyl group. preferable. The hydrolyzable group is preferably an alkenyloxy group, and an alkoxy group is particularly preferred from the viewpoint of mild hydrolyzability and easy handling.

When the fluorosilyl group represented by the formula (8) is exemplified, a silicon group having no hydrolyzable group other than fluorine or a fluorosilyl group in which R ¹¹ is a methyl group are preferable, and a trifluorosilyl group is more preferable.

The compound having a fluorosilyl group represented by the formula (8) 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 (8) at the terminal Examples thereof include polymer compounds such as siloxane, and preferred are fluorosilanes represented by the formula (7) and polymers having a fluorosilyl group represented by the formula (8) 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 photo-curable pressure-sensitive adhesive that exhibits rapid curing.

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

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, and 0.05 to 20 parts by mass with respect to 100 parts by mass in total of the A component and the B component. Is more preferable. When a high molecular compound having a number average molecular weight of 3,000 or more, such as a fluorinated polymer, is used as the silicon compound having an Si—F bond, the amount is preferably 0.01 to 80 parts by mass with respect to 100 parts by mass of the liquid AB component. 0.01 to 30 parts by mass is more preferable, and 0.05 to 20 parts by mass is even 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 (9) and fluorosilyl groups represented by the formula (8) In the case of using a low molecular weight organic silicon compound having a fluorosilyl group, an inorganic silicon compound having a fluorosilyl group, etc., the amount is preferably 0.01 to 10 parts by weight, and 0.05 to 5 parts by weight with respect to 100 parts by weight of the liquid AB component. More preferred.

(Fluorine compounds)
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.

The blending ratio of the fluorine-based compound is not particularly limited, but is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 5 parts by weight, and 0.001 to 2 parts by weight with respect to 100 parts by weight of the liquid AB component. Part is more preferred. These fluorine compounds may be used alone or in combination of two or more.

The photocurable pressure-sensitive adhesive can contain 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 a photocurable pressure-sensitive adhesive, when functioning as a pressure-sensitive adhesive that is post-cured (that is, converted into an adhesive), (B2) the liquid organic polymer contains a crosslinkable silicon group-containing organic polymer, and photocurable pressure-sensitive adhesive. It is preferable that the agent contains a silicon compound having a Si—F bond.

(D component: tackifying resin)
The tackifying resin as component D is not particularly limited, and examples thereof include resins having polar groups such as rosin ester resins, phenol resins, xylene resins, xylene phenol resins, terpene phenol resins, and aromatics having a relatively small polarity. Ordinary tackifying resins such as various petroleum resins such as aliphatic, aliphatic-aromatic copolymer systems, or alicyclic systems, or coumarone resins, low molecular weight polyethylene resins, terpene resins, and resins obtained by hydrogenating them. be able to. These may be used alone or in combination of two or more.

Specific examples of these resins include aromatic petroleum resins such as α-methylstyrene single polymer resin (FTR Zero series, Mitsui Chemicals), styrene monomer single polymer resin [FTR 8000 series, Mitsui 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.].

From the viewpoint of compatibility with the B component, the solubility parameter (hereinafter, abbreviated as “SP value” in principle) calculated by the Small method using Hoy's constant is preferably 7.9 to 11.0, 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 component B. 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 100 parts by mass of the A component, the B1 component, and / or the B2 component (when both the B1 component and the B2 component are used, the total of the A component, the B1 component, and the B2 component is 100 parts by mass). Is preferably 5 to 200 parts by weight, more preferably 10 to 150 parts by weight. 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.

(E component: polyfunctional monomer containing a photoradically polymerizable vinyl group, polyfunctional polymer containing a photoradically polymerizable vinyl group)
The photocurable pressure-sensitive adhesive according to the present invention can also contain a polyfunctional monomer from the viewpoint of ensuring the high-temperature pressure-sensitive adhesiveness. The more functional groups of the polyfunctional monomer, the greater the adhesive force of the photocurable adhesive at high temperatures. The functional group of the polyfunctional monomer is preferably bifunctional because the number of functional groups is a predetermined number or more, and the hardness when the photocurable pressure-sensitive adhesive is cured is 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 pressure-sensitive adhesive.

As the polyfunctional monomer, for example, (E) a compound having a radical photopolymerizable vinyl group is used. And as a compound which has (E) radical photopolymerizable vinyl group, the polyfunctional monomer which has various radical photopolymerizable vinyl groups 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, etc. to the photocurable pressure-sensitive adhesive. 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). Contains 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 adhesive. 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, dicyclopentanyl di (meth) Acrylate, polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxytetraethoxyphenyl) propane, etc. Trifunctional (meth) acrylate monomer such as bifunctional (meth) acrylate monomer, trimethylolpropane tri (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, dimethylolpropane tetra (meth) acrylate, pentaerythritol Tetra ( Data) acrylate, or pentaerythritol ethoxy tetra (meth) acrylate 4 or more functional groups of the (meth) acrylate monomers. A bifunctional (meth) acrylate monomer is preferable from the viewpoint of maintaining the flexibility of the photocurable adhesive, and a trifunctional (meth) acrylate monomer and a tetrafunctional or higher (meth) acrylate monomer from the viewpoint of good reactivity. Is preferred.

The blending amount of the polyfunctional (meth) acrylate monomer is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the component A, the component B1, and / or other monofunctional (meth) acrylate monomers. 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.

Polyfunctional (meth) acrylate polymers include polyether-based urethane (meth) acrylates (eg, “UV-3700B” and “UV-6100B” manufactured by Nippon Gosei Co., Ltd.), polyester-based urethane (meth) acrylates (eg, Japan) “UV-2000B”, “UV-3000B”, “UV-7000B” manufactured by Synthetic Co., Ltd. “KHP-11”, “KHP-17” manufactured by Negami Kogyo Co., Ltd.), non-aromatic polycarbonate urethane (meth) acrylate (for example, "Art Resin UN-9200A" manufactured by Negami Kogyo Co., Ltd.), acrylic (meth) acrylate (for example, "RC-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.) 1,2-polybutadiene-terminated urethane (meth) acrylate hydrogenated product (for example, “TEAI-1000” manufactured by Nippon Soda Co., Ltd.), 1,4-polybutadiene-terminated urethane (meth) acrylate (for example, “manufactured by Osaka Organic Chemical Co., Ltd.” BAC-45 "), polyisoprene-terminated (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 from the viewpoint of flexibility of the cured photocurable pressure-sensitive adhesive, preferably 3,000 to 45,000, and 5,000 to 20 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 of the photocurable adhesive.

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 component A, component B1, 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)
The photocurable pressure-sensitive adhesive of the present invention includes a conductive filler, an N-vinyl compound, a compound having a (meth) acrylamide group, a silane coupling agent, a photosensitizer, an extender, a plasticizer, if necessary. Moisture absorbers, curing catalysts, physical property modifiers that improve tensile properties, reinforcing agents, colorants, flame retardants, anti-sagging agents, antioxidants, anti-aging agents, UV absorbers, solvents, fragrances, pigments, dyes, Various additives such as a filler and a diluent may be added.

(Conductive filler)
As the conductive filler, carbon particles, metal particles such as silver, copper, nickel, gold, tin, zinc, platinum, palladium, iron, tungsten, molybdenum, solder, or alloy particles, or the surface of these particles such as metal Conductive particles such as particles prepared by covering with a conductive coating can be used. In addition, for example, polymer particles that are non-conductive particles composed of polyethylene, polystyrene, phenol resin, epoxy resin, acrylic resin, or benzoguanamine resin, or inorganic particles composed of glass beads, silica, graphite, or ceramic. Conductive particles obtained by applying a conductive coating such as metal to the surface can also be used.

As the shape of the conductive filler, various shapes (for example, a spherical shape, an ellipse, a cylindrical shape, a flake, a needle shape, a resin shape, a whisker, a flat plate, a granule, a crystal, an acicular shape, etc.) can be adopted. The conductive filler can also have a slightly rough or jagged surface. The shape of the conductive filler is not particularly limited. A combination of the particle shape, size, and / or hardness of the conductive filler can be used in the photocurable pressure-sensitive adhesive. Moreover, for the purpose of further improving the conductivity of the photocurable pressure-sensitive adhesive, it is preferable to combine a plurality of conductive fillers having different particle shapes, sizes, and / or hardnesses of the conductive filler. As an example, it is preferable to mix and use a granular conductive filler and a flaky conductive filler. In addition, the conductive filler to combine is not restricted to two types, Three or more types may be sufficient.

(N-vinyl compound having a vinyl group)
Examples of the N-vinyl compound having a vinyl group include N-vinylpyrrolidone and N-vinylcaprolactam. In the present invention, an N-vinyl compound is preferred from the viewpoint of reactivity and resistance to oxygen inhibition.

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

(Silane coupling agent)
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)
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.

(Photoaminosilane-generating compound)
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 photoaminosilane generating compounds 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 in which the photofunctional group is a p-nitrobenzyl group include 4-nitrobenzyl-N- [3- (trimethoxysilyl) propyl] carbamate. Examples of the photoaminosilane generating compound in which the photofunctional group is a benzyl group include 1- (3,5-dimethoxyphenyl) -1-methylethyl-N- [3- (trimethoxysilyl) propyl] carbamate. Examples of the photoaminosilane generating compound in which the photofunctional group is an oxime residue group include benzophenone O-{[3- (trimethoxysilyl) propyl]} oxime.

The mixing ratio of the silane coupling agent is not particularly limited, but is preferably 0.01 to 20% by mass, and more preferably 0.025 to 10% by mass in the photocurable adhesive. These silane coupling agents may be used alone or in combination of two or more.

(Moisture absorbent)
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.

(Other condensation reaction promoting catalysts)
As the other condensation reaction accelerating catalyst excluding the component (C) and the compound having a Si—F bond, known curing catalysts can be widely used, and are not particularly limited. For example, organometallic compounds, amines, fatty acids Organic acid phosphate compounds, and the like, 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 pressure-sensitive adhesive may be increased depending on the amount of the organotin compound added. Since the component (C) of the present invention and the compound having an Si—F bond act as a condensation reaction accelerating catalyst, when a curing catalyst other than these is used, it should be used within a range where the object and effect of the present invention can be achieved. preferable.

(Filler)
As the filler excluding the conductive 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 contained suitably in a photocurable adhesive as a filler, a spherical crosslinked resin filler is preferable. In addition, when using the photocurable adhesive which manufactures the peripheral part of a liquid crystal display device, etc. for the use for 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 size 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.

(Diluent)
The photocurable pressure-sensitive adhesive of the present invention can further contain a diluent. By blending the diluent, physical properties such as the viscosity of the photocurable pressure-sensitive adhesive 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 ester solvents such as acetyltriethyl citrate, and ketone solvents.

There is no particular restriction on the flash point of the diluent, but considering the safety of the photo-curing adhesive, it is desirable that the flash point of the photo-curing adhesive is high, and the less volatile substances from the photo-curing adhesive 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, a diluent having a high flash point tends to have a low dilution effect on the photocurable pressure-sensitive adhesive. Therefore, the flash point is preferably 250 ° C. or lower.

In consideration of both the safety and dilution effect of the photocurable adhesive, a saturated hydrocarbon solvent is preferable as the diluent, and normal paraffin and isoparaffin are more preferable. Normal paraffin and isoparaffin preferably have 10 to 16 carbon atoms.

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

(Method for producing photocurable pressure-sensitive adhesive)
The method for producing the photocurable pressure-sensitive adhesive is not particularly limited. For example, a predetermined amount of the A component, the B1 component and / or the B2 component, and the C 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 pressure-sensitive adhesive 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 pressure-sensitive adhesive according to the present invention is a photocurable pressure-sensitive adhesive that is cured by exerting light-sensitive properties and can be cured at room temperature (for example, 23 ° C.). Although it is preferably used as an agent, curing may be accelerated by heating as necessary.

The photocurable adhesive according to the present invention exhibits adhesiveness and is cured when irradiated with light. By this curing, a cured product of the photocurable pressure-sensitive adhesive can be obtained. Moreover, various adhesive containing products, such as an electronic circuit, an electronic component, a building material, a motor vehicle, can be manufactured using the photocurable adhesive which concerns on this invention.

Although there is no restriction | limiting in particular as conditions which irradiate light with respect to the photocurable adhesive 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.

For example, in the case of ultraviolet rays, the irradiation energy is preferably 10 to 20,000 mJ / cm ^2, more preferably 20 to 10,000 mJ / cm ^{2, and} still more preferably 50 to 5,000 mJ / cm ² . 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.

The method for applying the photocurable pressure-sensitive adhesive according to the present invention to the adherend is not particularly limited, but screen printing, stencil printing, roll printing, dispenser coating, spin coating and the like are preferably used.

Also, there is no limitation on the timing of application and light irradiation of the photocurable adhesive to the adherend. For example, after irradiating light to a photocurable adhesive, it joins with a to-be-adhered body and can manufacture a product (namely, adhesive body). Moreover, a photocurable adhesive can be apply | coated to a to-be-adhered body, a photocurable adhesive can be hardened by irradiating light, and a product can be manufactured.

Also, for example, when the adherends are bonded together, the photocurable adhesive according to the present invention is applied to at least one adherend (application step). In the coating step, the photocurable adhesive may be applied to one adherend, or the photocurable adhesive may be applied to each of both adherends. From the viewpoint of simplifying the coating process, the photocurable pressure-sensitive adhesive can be applied only to one adherend. Next, light is irradiated to this photocurable adhesive (light irradiation process). The photocurable pressure-sensitive adhesive exhibits adhesiveness by light irradiation. Subsequently, after the light irradiation, the other adherend is brought into contact with the photocurable adhesive which is applied to one adherend and irradiated with light. That is, the other adherend is bonded to one adherend by sandwiching the photocurable adhesive applied to the one adherend between the other adherends (bonding step). Then, the other adherend is bonded to one adherend (bonding step). Thereby, a product (that is, an adhesive body) in which adherends are bonded to each other is manufactured. However, as the other adherend, a protective member such as a protective sheet for the adhesive surface is excluded. This is because the photocurable pressure-sensitive adhesive used in the bonding method of the present invention is for on-site construction, and one adherend and the other adherend are directly bonded with the photocurable pressure-sensitive adhesive.

The photocurable pressure-sensitive adhesive according to the present invention is a fast-curing type photocurable pressure-sensitive adhesive excellent in workability and can be suitably used as a pressure-sensitive adhesive.

(Effect of embodiment)
Since the photocurable pressure-sensitive adhesive 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 adhesive exhibits quick adhesiveness by light irradiation. Therefore, according to the photocurable pressure-sensitive adhesive according to the present invention, after the photocurable pressure-sensitive adhesive is applied to one adherend and irradiated with light, the other adherend is applied to the photocurable pressure-sensitive adhesive that exhibits adhesiveness. Therefore, even when the adherend does not transmit light such as ultraviolet light, a plurality of adherends can be easily bonded together.

That is, the photocurable pressure-sensitive adhesive according to the present invention does not cure when it is not irradiated with active energy rays, and does not block from the outside air (that is, does not cover with a film or the like). It is a curable pressure-sensitive adhesive, and is a photo-curable pressure-sensitive adhesive having fast curability excellent in rising adhesiveness after irradiation with active energy rays. Therefore, a predetermined bonding time can be secured after light irradiation.

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

(Synthesis Example 1) 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 terminal 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. ^{As a result of 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 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 terminal 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. ^{As a result of 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 70.00 g of methyl methacrylate, 30.00 g of 2-ethylhexyl methacrylate, 12.00 g of 3-methacryloxypropyltrimethoxysilane, 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 terminal 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.

Next, 2.4 g of BF ₃ diethyl ether complex, 1.6 g of dehydrated methanol, 100 g of polymer A4, and 5 g of toluene were used, and a polyoxy group having a fluorosilyl group at the end was prepared according to the method of Synthesis Example 4 of WO2015-088021. An alkylene polymer (hereinafter referred to as a fluorinated polymer) was obtained. The 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. (M, 0.63 ppm) disappeared, and a broad peak appeared on the low magnetic field side (0.7 ppm-).

(Synthesis Example 5) Synthesis of crosslinkable silicon group-containing compound F1 which generates an amino group by light 15.3 parts of 2-nitrobenzyl alcohol and 344 parts of toluene were added to a flask and refluxed at about 113 ° C. for 60 minutes. Thereafter, 20.5 parts of 3-isocyanatopropyltrimethoxysilane was added dropwise and stirred for 5 hours. The compound (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 F1))). As a result of IR spectrum measurement of the photoaminosilane-generating compound F1, no —N═C═O bond was detected.

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, and a photocurable adhesive was added. 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. The B component includes a B1 component and a B2 component.
[Component A: Monoacrylate]
(2HPPA-M600A) 2-hydroxy-3-phenoxypropyl acrylate (Product name: M-600A, manufactured by Kyoeisha Chemical Co., Ltd.)
[B1 component: monofunctional (meth) acrylate]
(LA) Lauryl acrylate (Product name: Light acrylate LA, manufactured by Kyoeisha Chemical Co., Ltd.)
(2HEA) Hydroxyethyl acrylate (Product name: HEA, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
(2HBA) 2-hydroxybutyl acrylate (Product name: HOB-A, manufactured by Kyoeisha Chemical Co., Ltd.)
(ACMO) 4-acryloylmorpholine (Product name: ACMO, KJ Chemicals [B2 component: liquid organic polymer]
(PPG) polyether polyol (polyoxypropylene diol, Mw: 15,000, product name: Preminol S4015, manufactured by Asahi Glass Co., Ltd.)
(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: IRGACURE 379EG, manufactured by BASF)
(Irgacure TPO) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Product name: IRGACURE TPO, manufactured by BASF)
[D component: tackifying resin]
(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.)
[E component: polyfunctional (meth) acrylate]
(UV3300B) photo-radical vinyl group-containing polyfunctional polymer (urethane acrylate, Mw: 13,000, Tg: -30 ° C., functional group number: 2, product name: UV3300B, manufactured by Nippon Synthetic Chemical Co., Ltd.)
[Compound with Si—F bond]
(Fluorinated polymer) Fluorinated polymer synthesized in Synthesis Example 4 (BF ₃ -MEA) Boron trifluoride monoethylamine

(Peel strength test)
The photocurable adhesive according to Example 1 was applied to the first adherend (PET film) using a glass rod. The thickness of the photocurable pressure-sensitive adhesive is 250 μm. Next, the photocurable adhesive 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 adhering material (adhesive material made of polymethyl methacrylate resin (PMMA)) having an area of 25 mm × 80 mm is sandwiched between the UV-irradiated photocurable adhesive. A pressure was applied using a 2 kg roller. After the pressure was applied, 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 Table 1. In Table 1, the unit of peel strength is “N / 25 mm”.

(Surface curing (finger touch) test)
The photocurable pressure-sensitive adhesive according to Example 1 was applied to an adherend (PET film) using a glass rod. The thickness of the photocurable pressure-sensitive adhesive is 250 μm. Next, the photocurable pressure-sensitive adhesive on the adherend was irradiated with ultraviolet rays (UV) [irradiation conditions: UV-LED lamp (wavelength 365 nm, illuminance: 1000 mW / cm ² ), integrated light amount: 3000 mJ / cm ² ]. Immediately after UV irradiation, surface curability was tested by finger touch in an environment of 23 ° C. and 50% RH in a dark room. The test results are shown in Table 1. In Table 1, “◯” indicates that the uncured material does not adhere to the finger, “△” indicates that the material is slightly adhered, “×” indicates that the liquid material remains on the finger surface, and “Uncured” if the material does not cure. ".

(Examples 2 to 6 and Comparative Examples 1 to 6)
As shown in Table 1, after obtaining the photocurable pressure-sensitive adhesive by the same method as in Example 1 except that the compounding substances were changed, the characteristics of the obtained photocurable pressure-sensitive adhesive were evaluated in the same manner as in Example 1. did. The results are shown in Table 1.

As shown in Table 1, the photocurable pressure-sensitive adhesives according to the examples were curable in a short time and exhibited excellent rising adhesiveness. Furthermore, the photocurable adhesive which concerns on an Example showed the outstanding peeling strength. In addition, although the comparative example 6 was hardened | cured in the surface-curing property test, adhesiveness did not exist.

(Example 7)
A photocurable pressure-sensitive adhesive that was easily post-cured was prepared in the same manner as in Example 1 at the blending ratio shown in Table 2.

In Table 2, the unit of the compounding amount of each compounding substance is “g”. The details of the compounding substances are as follows. All of B component, C component, D component, E component, fluorinated polymer, and BF ₃ except ECA, KBM5103, P-EO-A, and 4HBA are the same as in Table 1.
(2HPPA-PGA) 2-hydroxy-3-phenoxypropyl acrylate (Product name: PGA, manufactured by Daiichi Kogyo Seiyaku 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.)
(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.)
(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.)
(UV3700B) photo-radical vinyl group-containing polyfunctional polymer; (urethane acrylate, Mw: 38,000, Tg: −6 ° C., functional group number: 2, product name: UV3700B, manufactured by Nippon Synthetic Chemical Co., Ltd.)
(Photoaminosilane) Photoaminosilane-generating compound F1 synthesized in Synthesis Example 5

(Peel adhesion strength test)
The photocurable adhesive according to Example 7 was applied to the first adherend (PET film) using a glass rod. The thickness of the photocurable pressure-sensitive adhesive is 200 μm. Next, the photocurable adhesive 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 adhesive. Bonding was performed on the adherend, and pressure was applied using a 2 kg roller. After the pressure was applied, 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 2.

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 adhesive, and the pressure is applied 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 “Peel Test 2” in Table 2. In Table 2, the unit of peel adhesion strength is “N / 25 mm”.

(Shear bond strength test)
The photocurable adhesive which concerns on Example 7 was apply | coated to the 1st to-be-adhered material (the aluminum adherend which performed the sulfuric acid alumite process) using the glass rod. The thickness of the photocurable pressure-sensitive adhesive is 200 μm. Next, the photocurable adhesive 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 adhering material (aluminum adhering material subjected to sulfuric acid alumite treatment) with an area of 25 mm × 25 mm is sandwiched between the UV-irradiated photocurable adhesive. 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 2.

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-irradiated photocurable adhesive with 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 2. In Table 2, the unit of tensile shear bond strength is “N / mm ² ”.

In the peel test and the shear test of Table 2, 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 8 to 15 and Comparative Examples 7 to 10)
As shown in Table 2, after obtaining a photocurable pressure-sensitive adhesive that is easily post-cured in the same manner as in Example 7 except that the compounding substances were changed, the characteristics of the resulting photocurable pressure-sensitive adhesive were measured in Example 7. And evaluated in the same manner. The results are shown in Table 2. In addition, the measurement value “0” of the evaluation of Comparative Example 10 (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 2, it was shown that all of the photocurable pressure-sensitive adhesives according to the examples quickly exhibited excellent tackiness immediately after UV irradiation, and exhibited superior adhesiveness due to changes over time.

(LED chip bonding test)
Fig.1 (a) and (b) show the outline | summary of the printed circuit board used for the LED chip bonding test, and an LED chip. FIG. 2 shows an outline of the process of bonding the LED chip to the printed board. Note that FIG. 2 is described using the AA cross section in FIG. 1 and 2 are schematic views and do not correspond to actual shapes and dimensions.

In this test, an LED chip bonding test was performed using the photo-curable adhesive according to Example 1. Specifically, first, as shown in FIGS. 1A and 2A, the wiring pattern 12 and wiring pattern 14 made of copper, the mounting portion 16 and mounting portion 18 made of copper, and the terminal electrode made of copper A printed circuit board 10 on which 20 and terminal electrodes 22 were printed was prepared. Further, an LED chip 30 (manufactured by Linkman, product model number: HT17-21SRWC, emission wavelength when forward current is 20 mA: 624 nm to 630 nm) as shown in FIG. 1B was prepared. The LED chip 30 is electrically connected to a chip substrate 32, an LED element (not shown) mounted on the chip substrate 32, and an anode electrode of the LED element, and is provided at one end of the chip substrate 32. A connection electrode 34, a connection electrode 36 that is electrically connected to the cathode electrode of the LED element and is provided at the other end of the chip substrate 32, and a sealing portion 38 that seals the LED element are provided.

Next, a metal mask 40 having an opening 40a was placed on the printed board 10. Specifically, as shown in FIG. 2B, the metal mask 40 is placed on the printed circuit board 10 so that the openings 40 a correspond to the mounting

parts

16 and 18 of the printed circuit board 10. Then, a moisture curable conductive adhesive layer 42 and a moisture curable conductive adhesive layer 44 made of a moisture curable conductive adhesive (modified silicone, product name: SX-ECA48, manufactured by Cemedine Co., Ltd.) are formed by screen printing. (See FIG. 2 (c)). The thickness of the moisture curable conductive adhesive layer 42 and the moisture curable conductive adhesive layer 44 was set to 115 μm.

Subsequently, as shown in FIG. 2 (d), the photocurable adhesive 46 according to Example 1 was dispensed with a thickness of 100 μm between the mounting portion 16 and the mounting portion 18 of the printed circuit board 10. Then, the photocurable adhesive 46 on the printed circuit board 10 was irradiated with ultraviolet rays (UV) (irradiation conditions: UV-LED lamp (wavelength 365 nm, illuminance 1000 mW / cm ² ), irradiation time: 3 seconds)). Immediately after UV irradiation, the LED chip 30 was mounted on the printed circuit board 10 as shown in FIG. In this case, the connection electrode 34 is in contact with the moisture curable conductive adhesive layer 42 on the mounting portion 16, the connection electrode 36 is in contact with the moisture curable conductive adhesive layer 44 on the mounting portion 18, and the LED chip. It mounted so that it might become a position where the photocurable adhesive 46 contact | connects the bottom part except the connection electrode 34 and the connection electrode 36 of 30.

</ RTI> Immediately after mounting, a force was applied to the LED chip 30 (the direction in which the force was applied is the shear direction). As a result, it was confirmed that the LED chip 30 was sufficiently fixed to the printed circuit board 10.

Thereafter, the moisture curable conductive adhesive layer 42 and the moisture curable conductive adhesive layer 44 are cured by being left for 24 hours in an environment of 23 ° C. and 50% RH, and then the terminal electrode 20 and the terminal electrode 22 are mounted on the LED chip 30. When a current of 20 mA was applied through the LED chip 30, it was confirmed that the LED chip 30 emitted red light.

The embodiments and examples of the present invention have been described above. However, the embodiments and examples described above do not limit the invention according to the claims. In addition, 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.

DESCRIPTION OF SYMBOLS 10 Printed

circuit board

12, 14

Wiring pattern

16, 18 Mounting

part

20, 22 Terminal electrode 30 LED chip 32

Chip board

34, 36 Connection electrode 38 Sealing part 40 Metal mask

40a Opening part

42, 44 Moisture curable conductive adhesive layer 46 Photo-curable adhesive

Claims

A method of bonding a plurality of adherends,
(A) a monoacrylate represented by the following general formula (1);
(B1) monofunctional (meth) acrylate, and (B2) at least one organic compound selected from the group consisting of liquid organic polymers;
(C) a photoinitiator;
An application step of applying a photocurable pressure-sensitive adhesive that exhibits adhesiveness by light irradiation containing at least one adherend;
A light irradiation step of irradiating light to the photocurable pressure-sensitive adhesive applied to the one adherend;
The step of adhering the other adherend (excluding the protective sheet for the adhesive surface as the other adherend) to the photocurable pressure-sensitive adhesive applied to the one adherend and irradiated with the light A bonding method comprising:

(In general formula (1), R 1 represents a hydrogen atom or a methyl group, and R 2 to R 6 are each independently a hydrogen atom or a substituent.)
The adhesion method according to claim 1, wherein the photocurable pressure-sensitive adhesive further contains (D) a tackifying resin.
The adhesion method according to claim 1 or 2, wherein the photocurable pressure-sensitive adhesive further contains (E) a compound containing two or more photoradically polymerizable vinyl groups.
The bonding method according to claim 3, wherein the compound (E) containing two or more photo-radically polymerizable vinyl groups is a polymer.
The bonding method according to any one of claims 1 to 4, wherein the (B2) liquid organic polymer is a polymer having a crosslinkable silicon group.
An bonded body produced by using the bonding method according to any one of claims 1 to 5.
It is a photocurable pressure-sensitive adhesive that exhibits adhesiveness by light irradiation,
(A) a monoacrylate represented by the following general formula (1);
(B1) monofunctional (meth) acrylate, and (B2) at least one organic compound selected from the group consisting of liquid organic polymers;
(C) A photocurable adhesive for on-site construction containing a photoinitiator.

(In general formula (1), R 1 represents a hydrogen atom or a methyl group, and R 2 to R 6 are each independently a hydrogen atom or a substituent.)