KR20170099840A - Photocurable composition - Google Patents

Abstract

A dual cure type photo-curing composition using moisture curing and photo curing, which is capable of taking a sufficient working time because the curing does not proceed prior to light irradiation, thereby producing a cured product having excellent toughness immediately after light irradiation, The present invention provides a dual cure type photo-curing composition which is completely cured and does not generate a corrosive acid relatively quickly while securing a suitable bonding time. (A) a crosslinkable silicon group-containing organic polymer, (B) a photo-base generator, (C1) a silicon compound having a Si-F bond, and (C2) a boron fluoride, a complex of boron trifluoride, And an alkali metal salt of a polyfunctional fluorine compound, and (D) a polyfunctional compound having at least one (meth) acryloyl group in one molecule.

Description

[0001] PHOTOCURABLE COMPOSITION [0002]

The present invention relates to a dual cure type photocurable composition using moisture curing and active energy ray (light) curing. Particularly, the present invention relates to a dual cure type photo-curable composition which is excellent in temporary fixation of an adherend immediately after light irradiation and can be cured in a short time.

An organic polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having a silicon-containing group capable of crosslinking by forming a siloxane bond (hereinafter also referred to as a " crosslinkable silicon group ") may be a liquid And is capable of crosslinking by the formation of siloxane bonds accompanied by the hydrolysis reaction of the crosslinkable silicon group by action of moisture in air or the like even at room temperature to obtain a cured product. For this reason, the polymer is widely used for sealing materials, adhesives, paints and the like. Examples of the polymer having a crosslinkable silicon group include a polyoxyalkylene polymer and a (meth) acrylic ester polymer.

Patent Document 1 discloses an adhesive composition containing a polymer having a hydrolyzable silyl group (corresponding to a crosslinkable silicon group) and a compound having a photopolymerizable polymerizable group. The polymer having a hydrolyzable silyl group is a polymer which is crosslinked and cured by wetting in the air and the like, and the compound having a photopolymerizable polymerizable group is a compound which increases the molecular weight by light irradiation. This adhesive composition is a liquid phase that can be applied before light irradiation. When irradiated with light, the compound having a photopolymerizable polymerizable group becomes a polymer, and the adherend can be temporarily fixed, so that the adherend can be fixed have. If left untouched, the hydrolyzable silyl group-containing polymer contained in the adhesive composition is cured to finally obtain an adhesive having a high strength.

The curable composition obtained by using a compound having different curing mechanisms in combination is called a dual cure type of moisture curing and photo curing in the case of Patent Document 1 and is used for adhesion or the like capable of tentative fixing even when there is no temporary fixing jig.

The polymer having a crosslinkable silicon group is cured by moisture under the action of a curing catalyst, but when the polymer is applied thinly on the adherend (for example, 500 m or less) by using the polymer as an adhesive, So that it penetrates into the inside instantaneously, and the curing progresses at the time of application, making it impossible to perform the bonding work. Further, when a catalyst having a small catalytic activity is used, curing is difficult to proceed and it takes time to complete curing. When the adhesive is thinly applied as described above, it is difficult to select a suitable curing catalyst for a polymer having a crosslinkable silicon group.

Patent Document 2 discloses an adhesive composition using a photoacid generator as a cure catalyst for a polymer having a dual cure type and a crosslinkable silicon group. In this composition, the generated acid acts as a curing catalyst. In the adhesive composition disclosed in Patent Document 1, the curing of the polymer having a crosslinkable silicon group starts from the time of application of the adherend. On the other hand, in the adhesive composition of Patent Document 2, since acid which is a curing catalyst of a polymer having a crosslinkable silicon group is produced by light irradiation, the curing of the polymer having a crosslinkable silicon group does not proceed until the light irradiation. For this reason, according to the adhesive composition described in Patent Document 2, B-staging can be performed quickly after ultraviolet irradiation, and problems such as slumping can be avoided.

However, in the adhesive composition described in Patent Document 2, since a photoacid generator is used, when an amine, an alkaline substance, or the like is mixed, an active acid catalyst generated from the photoacid generator reacts, and the photopolymerization is remarkably inhibited do. This is not only the case where a basic adhesive agent, filler or the like is added to the composition, but also when the adherend contains a basic substance. Therefore, as described in the example of Patent Document 2, the adhesive composition described in Patent Document 2 does not exhibit sufficient adhesive force immediately after UV irradiation, resulting in poor adhesiveness, and the adherend is also limited. Further, there is a problem that rust is generated, so that it can not be applied to the adhesion of metal.

Patent Document 1: Japanese Patent Application Laid-Open No. 2001-139893 Patent Document 2: Japanese Patent Publication No. 2009-530441

Accordingly, it is an object of the present invention to provide a dual cure type photo-curable composition using moisture curing and photo curing, which can not sufficiently cure before light irradiation and can take a sufficient working time, Curing type composition which does not generate a completely cured and corrosive acid relatively quickly while ensuring a suitable bonding time after light irradiation.

(C) a silicon compound having a Si-F bond, and (C2) a fluorine-containing organic compound having a fluorine-containing group, At least one fluorine-based compound selected from the group consisting of boron, complex of boron trifluoride, a fluorinating agent, and an alkali metal salt of a polyfunctional fluorine compound, (D) a compound having at least one (meth) acryloyl group in one molecule There is provided a photocurable composition containing a functional compound.

It is also preferable that the photo-curable composition further comprises a crosslinkable silicon group-containing compound which generates, by (E) light, at least one amino group selected from the group consisting of a primary amino group and a secondary amino group .

Further, it is preferable that the photocurable composition further comprises (F) a monofunctional compound having a photopolymerizable unsaturated group.

The photocurable composition preferably further comprises (G) a tackifier resin.

In the photocurable composition, it is preferable that (A) the crosslinkable silicon group-containing organic polymer is at least one selected from the group consisting of a crosslinkable silicon group-containing polyoxyalkylene polymer and a crosslinkable silicon group-containing (meth) More than species are suitable.

Further, in the photocurable composition, it is preferable that the photobase generator (B) is a photolatent tertiary amine. Herein, a substance which generates an amine compound by the action of an active energy ray is referred to as a photocurable amine compound. Also, by the action of an active energy ray, a substance capable of generating an amine compound having a primary amino group is referred to as a phototolerant primary amine, and a substance capable of generating an amine compound having a secondary amino group, , And a substance that generates an amine compound having a tertiary amino group is referred to as a photolatent tertiary amine.

(A) a polymer having a crosslinkable silicon group and a photo radically polymerizable vinyl group in the molecule (provided that the polymer having a Si-F bond is a And (a-2) an organic polymer having a crosslinkable silicon group other than (a-1).

The present invention also provides a cured product formed by irradiating light to the photo-curing composition in order to achieve the above object.

Further, in order to achieve the above object, the present invention provides an article produced using the photo-curable composition. Further, in order to achieve the above object, the present invention provides an article using the photocurable composition as an adhesive. In order to achieve the above object, the present invention also provides an electronic device product using the photo-curable composition.

In order to achieve the above object, the present invention provides a method for rework of electronic equipment, comprising the steps of: (A) preparing a liquid molding gaskets for electronic equipment, comprising: (A) an organic polymer containing a crosslinkable silicon group; (C1) a silicon compound having Si-F bonds, and (D) a step of preparing a field-shaping mold liquid gasket containing a polyfunctional compound having at least one (meth) acryloyl group in one molecule (B) applying a liquid gasket to a place where one housing member of the electronic apparatus is to be sealed in an uncured state, irradiating an active energy ray and fitting the other housing member, and (c) There is provided a method of reworking an electronic device including a step of removing a housing member of an electronic device requiring a rear work and replacing the internal parts.

According to the present invention, there is provided a dual cure type photo-curing composition using moisture curing and photo curing, wherein curing does not proceed prior to light irradiation, so that a sufficient working time can be taken and a cured product having excellent toughness And can provide a dual cure type photo-curable composition that is completely cured relatively quickly and does not generate a corrosive acid while securing a suitable bonding time after light irradiation.

Embodiments of the present invention will be described below, but these are merely illustrative, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.

The photo-curing composition according to the present embodiment comprises (A) an organic polymer containing a crosslinkable silicon group, (B) a photo-base generator, (C1) a silicon compound having Si-F bonds and / or (C2) 3 At least one fluorine-based compound selected from the group consisting of boron fluoride, a complex of boron trifluoride, a fluorinating agent and an alkali metal salt of a polyfunctional fluorine compound, (D) a compound having at least one (meth) acryloyl group in one molecule ≪ / RTI > In the description of the present embodiment, the photocurable composition according to the present embodiment may be referred to as " a formulation relating to this embodiment ".

[(A) Organic polymer containing a crosslinkable silicon group]

The organic polymer having a crosslinkable silicon group (A) is not particularly limited as long as it is an organic polymer having a crosslinkable silicon group. In the present embodiment, an organic polymer having a main chain other than a polysiloxane and having various main chain skeletons except for polysiloxane is contained or generated in a low molecular weight cyclic siloxane which is easy to obtain and which is a cause of contact trouble in the field of electric use It is suitable in that it does not. The organic polymer (A) containing a crosslinkable silicon group may have a photo-radical polymerizable vinyl group together with a crosslinkable silicon group. (A) the crosslinkable silicon group-containing organic polymer further contains a photo-radical polymerizable vinyl group in the molecule, the initial tackiness and / or flexibility of the photocurable composition of this embodiment can be more easily maintained, Heat resistance due to curing can be further improved. In the present embodiment, a polymer having a crosslinkable silicon group and a photo radically polymerizable vinyl group (except those having a Si-F bond) is referred to as a component (a-1) The organic polymer having a crosslinkable silicon group is referred to as (a-2) component. As the organic polymer containing a crosslinkable silicon group (A), the component (a-1) and / or the component (a-2) may be used.

Specific examples of the main chain skeleton of the crosslinkable silicon group-containing organic polymer (A) include polyoxyalkylene type polymers such as polyoxypropylene, polyoxytetramethylene and polyoxyethylene-polyoxypropylene copolymer; Ethylene-propylene copolymer, polyisobutylene, polyisoprene, polybutadiene, and hydrogenated polyolefin-based polymers obtained by hydrogenating these polyolefin-based polymers; A polyester polymer obtained by condensation of a dibasic acid such as adipic acid and glycol or ring-opening polymerization of lactones; (Meth) acrylate polymers obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate; Vinyl polymers obtained by radical polymerization of monomers such as (meth) acrylic acid ester monomers, vinyl acetate, acrylonitrile and styrene; A graft polymer obtained by polymerizing a vinyl monomer in an organic polymer; Polysulfide based polymers; Polyamide-based polymers; Polycarbonate-based polymers; Diallyl phthalate-based polymers, and the like. These skeletons may be contained singly in the (A) organic polymer containing a crosslinkable silicon group, or two or more kinds thereof may be contained in blocks or randomly.

In addition, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene and hydrogenated polybutadiene, polyoxyalkylene-based polymers and (meth) acrylate-based polymers are relatively low in glass transition temperature, Is preferable. Further, the polyoxyalkylene polymer and (meth) acrylate polymer are particularly preferable in that they are highly moisture-permeable and excellent in deep-part curability when they are made into a one-pack type composition.

(A) The crosslinkable silicon group of the crosslinkable silicon group-containing organic polymer is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond. As the crosslinkable silicon group, for example, a group represented by the formula (1) is suitable.

In formula (1), R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An aralkyl group, a triorganosiloxy group represented by R ¹ ₃ SiO- (wherein R ¹ is as defined above), or a -CH ₂ OR ¹ group (R ¹ is as defined above). In addition, R ¹ is, at least one hydrogen atom, halogen, -OR on the carbon atom of the third position from the first position ^{41, -NR 42 R 43, -N} = R 44, -SR 45 (R 41, R 42, R ⁴³ and R ⁴⁵ each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having no substituent, R ⁴⁴ is a hydrocarbon group having 1 to 20 carbon atoms or a bivalent substituent having no substituent A perfluoroalkyl group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a cyano group. Of these, R ¹ is preferably a methyl group. If R ¹ is present two or more, plural R ¹ may be the same or different is good. X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, plural Xs may be the same or different. a is an integer of 0, 1, 2 or 3; In view of curability, in order to obtain a curable composition having a sufficient curing rate, a is preferably 2 or more, and more preferably 3 in the formula (1).

The hydrolyzable group or hydroxyl group may be bonded to one silicon atom in a range of 1 to 3. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different. The number of silicon atoms forming the crosslinkable silicon group may be one or two or more, and in the case of silicon atoms connected by a siloxane bond or the like, about 20 silicon atoms may be used.

The hydrolyzable group represented by X is not particularly limited as long as it is other than an F atom. Examples thereof include an alkoxy group, an acyloxy group, an amino group, an amide group, an aminooxy group, and an alkenyloxy group. Of these, an alkoxy group is preferable from the viewpoint that the hydrolytic property is mild and easy to handle. Of the alkoxy groups, the smaller the number of carbon atoms is, the higher the reactivity is, and the more the number of carbon atoms is, the lower the reactivity is, such as methoxy> ethoxy> propoxy. The methoxy group or the ethoxy group is usually used although it can be selected according to the purpose or the purpose.

Examples of the specific structure of the crosslinkable silicon group include trialkoxysilyl groups such as trimethoxysilyl group and triethoxysilyl group [-Si (OR) ₃ ], methyldimethoxysilyl group and methyldiethoxysilyl group. Alkoxysilyl group [-SiR ¹ (OR) ₂ ], and trialkoxysilyl group [-Si (OR) ₃ ] is more preferable in view of high reactivity, and trimethoxysilyl group is more suitable. Wherein R is an alkyl group such as a methyl group or an ethyl group.

The crosslinkable silicon group may be used alone or in combination of two or more. The crosslinkable silicon group may be present either on the main chain or side chain or anywhere. A plurality of crosslinkable silicon groups represented by the general formula (1) may be connected to each other. In this case, the number of silicon atoms forming the crosslinkable silicon group is one or more, but in the case of a silicon atom bonded by a siloxane bond or the like, the number of silicon atoms is preferably 20 or less. Examples of the photo-radical polymerizable vinyl group include (meth) acryloyl group-containing groups such as (meth) acryloyloxy groups.

The organic polymer having a crosslinkable silicon group and the organic polymer having a crosslinkable silicon group and a photo radically polymerizable vinyl group may each have a straight chain or a branched chain and the number average molecular weight thereof is preferably 500 to 100,000 in terms of polystyrene in terms of GPC , More preferably from 1,000 to 50,000, and particularly preferably from 3,000 to 30,000. If the number average molecular weight is less than 500, it tends to be inadequate in terms of the elongation property of the cured product. When the number average molecular weight is more than 100,000, it tends to be inadequate in view of workability because of high viscosity.

In order to obtain a rubber-like cured product having a high strength and a high elongation and exhibiting a low elastic modulus, a crosslinkable silicone group contained in an organic polymer having a crosslinkable silicon group, a crosslinked silicone group contained in an organic polymer having a crosslinkable silicon group and a photo- The number of the silicon-containing group and the photo-radically polymerizable vinyl group is preferably 0.8 or more, preferably 1.0 or more, and more preferably 1.1 to 5, on the average in one molecule of the polymer. When the number of the crosslinkable silicon groups contained in the molecule and the number of the photo-radical polymerizable vinyl groups are less than 0.8 on average, the curability becomes insufficient and it becomes difficult to exhibit good rubber elastic behavior. The crosslinkable silicon group and the photo radically polymerizable vinyl group may be at the terminal or the end of the main chain of the organic polymer molecular chain or may be present at both ends thereof. Particularly, when the crosslinkable silicon group is present only at the end of the main chain of the molecular chain, since the effective mesh length of the organic polymer component contained in the finally formed cured product becomes long, the rubber- It becomes easy to obtain the cargo.

The polyoxyalkylene polymer is essentially a polymer having a repeating unit represented by the formula (2).

-R ² -O- (2)

In the formula (2), R ² is a linear or branched alkylene group having 1 to 14 carbon atoms, preferably a linear or branched alkylene group having 1 to 14 carbon atoms, a linear or branched alkyl group having 2 to 4 carbon atoms Rhenylene is more preferable.

Specific examples of the repeating unit represented by the formula (2)

_{-CH 2 O-, -CH 2 CH 2} O-, -CH 2 CH (CH 3) O-, -CH 2 CH (C 2 H 5) O-, -CH 2 C (CH 3) 2 O-, -CH ₂ CH may be mentioned ₂ CH ₂ CH ₂ O- and the like. The backbone skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit or two or more types of repeating units.

Examples of the synthesis method of the polyoxyalkylene polymer include 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, but there is no particular limitation. According to the polymerization method using a double metal cyanide complex catalyst, a polyoxyalkylene polymer having a high molecular weight and a narrow molecular weight distribution with a number average molecular weight of 6,000 or more and an Mw / Mn of 1.6 or less can be obtained.

The main chain skeleton of the polyoxyalkylene polymer may contain other components such as a urethane bonding component. Examples of the urethane bonding component include aromatic polyisocyanates such as toluene (tolylene) diisocyanate and diphenylmethane diisocyanate; And isophorone diisocyanate, and a polyoxyalkylene-based polymer having a hydroxyl group.

A functional group having reactivity with the functional group and a compound having a crosslinkable silicon group and / or a photo radically polymerizable vinyl group are reacted with a polyoxyalkylene polymer having a functional group such as an unsaturated group, hydroxyl group, epoxy group or isocyanate group in the molecule , A crosslinkable silicon group and / or a photo radically polymerizable vinyl group can be introduced into the polyoxyalkylene polymer (hereinafter referred to as a polymer reaction method).

As a specific example of the polymer reaction method, hydrosilane having a crosslinkable silicon group or mercapto compound having a crosslinkable silicon group is allowed to act on the unsaturated group-containing polyoxyalkylene polymer to form a hydrosilylation or a mercapto group, And a method of obtaining an oxyalkylene-based polymer. The unsaturated group-containing polyoxyalkylene polymer can be obtained by reacting an organic polymer having a functional group such as a hydroxyl group with an active group exhibiting reactivity with the functional group and an organic compound having an unsaturated group to obtain an unsaturated group-containing polyoxyalkylene polymer .

As another specific example of the polymer reaction method, there are a method of reacting a polyoxyalkylene polymer having a hydroxyl group at the terminal thereof with a compound having an isocyanate group and a crosslinkable silicon group and / or a photo radical polymerizable vinyl group, Group is reacted with a compound having an active hydrogen group such as a hydroxyl group or an amino group, and a crosslinkable silicon group and / or a photo radically polymerizable vinyl group. When the isocyanate compound is used, a polyoxyalkylene polymer having a crosslinkable silicon group and / or a photo radically polymerizable vinyl group can be easily obtained.

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

The saturated hydrocarbon-based polymer is a polymer substantially free of other carbon-carbon unsaturated bonds except for the aromatic ring. The polymer forming the skeleton may be obtained by polymerizing (1) 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 Or by hydrogenating the diene compound and the olefin compound after copolymerization of the diene compound and the olefin compound. The isobutylene-based polymer and the hydrogenated polybutadiene-based polymer are preferable because they can easily introduce a functional group at the terminal, easily control the molecular weight, and can increase the number of terminal functional groups, and an isobutylene polymer is particularly preferable . When the main chain skeleton is a saturated hydrocarbon polymer, it has characteristics of excellent heat resistance, weather resistance, durability and moisture barrier property.

The isobutylene polymer may be formed entirely of isobutylene units, or may be a copolymer with other monomers. In view of rubber properties, a polymer containing 50 mass% or more of repeating units derived from isobutylene is preferable, a polymer containing 80 mass% or more is more preferable, and a polymer containing 90 to 99 mass% is particularly preferable .

As the synthesis method of the saturated hydrocarbon polymer, various polymerization methods can be mentioned. In particular, various living polymerization have been developed. In the case of a saturated hydrocarbon polymer, particularly an isobutylene polymer, it can be easily produced by an initiator polymerization (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1997, vol. 15, p. 2843) Can be manufactured. According to this polymerization method, a polymer having a molecular weight of about 500 to 100,000 can be polymerized at a molecular weight distribution of 1.5 or less, and various functional groups can be introduced at the molecular end.

Examples of a method for producing a saturated hydrocarbon polymer having a crosslinkable silicon group and / or a photo radically polymerizable vinyl group include a cation polymerization method using a combination of an organic halogen compound which generates stable carbon cations and a Friedel Crafts acid catalyst as a copolymerization initiator . As an example, there can be mentioned the Inner method disclosed in Japanese Patent Publication No. Hei 4-69659.

The saturated hydrocarbon polymer having a crosslinkable silicon group and / or a photo radically polymerizable vinyl group may be used singly or in combination of two or more.

As the (meth) acrylic acid ester-based monomer constituting the main chain of the (meth) acrylic acid ester-based polymer, various monomers can be used. (Meth) acrylic acid-based monomers such as acrylic acid; Acrylic acid alkyl ester monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and stearyl (meth) acrylate; Alicyclic (meth) acrylate ester-based monomers; Aromatic (meth) acrylate monomers; (Meth) acrylic acid ester monomers such as 2-methoxyethyl (meth) acrylate; silyl group-containing (meth) acrylate-based monomers such as? - (methacryloyloxypropyl) trimethoxysilane and? - (methacryloyloxypropyl) dimethoxymethylsilane; (Meth) acrylic acid derivatives; Fluorine-containing (meth) acrylic acid ester-based monomers and the like.

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

These may be used alone or in combination. From the viewpoint of the physical properties of the product and the like, a polymer composed of a (meth) acrylic acid-based monomer is preferable. Further, a (meth) acrylic acid ester polymer in which one or more (meth) acrylic acid alkyl ester monomers are used and, if necessary, other (meth) acrylic acid monomers are used in combination is more preferable. In addition, the number of silicon groups in the (meth) acrylic ester polymer (A) can be controlled by using a silyl group-containing (meth) acrylate monomer in combination. From the viewpoint of good adhesiveness, a methacrylic ester polymer composed of a methacrylic ester monomer is particularly preferable. In addition, when imparting low viscosity, imparting flexibility, and imparting tackiness, it is preferable to use an acrylic acid ester monomer in a timely manner. In the present embodiment, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

A method for producing the (meth) acrylic ester polymer is not particularly limited, and for example, a radical polymerization method using a radical polymerization reaction can be used. Examples of the radical polymerization method include a radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator, a method in which a reactive silyl group and / or a photo radical polymerizable vinyl group is introduced at a controlled position such as a terminal A controlled radical polymerization method. However, the polymer obtained by the free radical polymerization method using an azo compound, peroxide or the like as a polymerization initiator generally has a molecular weight distribution value of 2 or more and a higher viscosity. Therefore, in order to obtain a (meth) acrylic acid ester polymer having a narrow molecular weight distribution and a low viscosity as a (meth) acrylic acid ester polymer and having a crosslinking functional group at the molecular chain end at a high ratio, it is preferable to use a controlled radical polymerization method Do.

Examples of the controlled radical polymerization method include a free radical polymerization method using a chain transfer agent having a specific functional group and a living radical polymerization method, and a reversible Addition-Fragmentation chain Transfer (RAFT) polymerization method, a transition metal complex A living radical polymerization method such as a transition-metal-mediated living radical polymerization method is more preferable. The reaction using a thiol compound having a reactive silyl group and the reaction using a thiol compound having a reactive silyl group and a metallocene compound are also suitable.

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

These organic polymers having a crosslinkable silicon group and / or a photo radically polymerizable vinyl group may be used alone or in combination of two or more. Specifically, a polyoxyalkylene polymer having a crosslinkable silicon group and / or a photo radically polymerizable vinyl group, a saturated hydrocarbon polymer having a crosslinkable silicon group and / or a photo radically polymerizable vinyl group, and a crosslinkable silicon group and / Or a (meth) acrylate ester polymer having a photo-radically polymerizable vinyl group may be used as the organic polymer.

As a method for producing an organic polymer in which a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic ester polymer having a crosslinkable silicon group are blended, various methods can be mentioned. For example, a crosslinkable silicon group, and the molecular chain is substantially composed of a compound represented by the formula (3):

-CH ₂ -C (R ³ ) (COOR ⁴ ) - ... (3)

(Wherein R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group having 1 to 5 carbon atoms), and (meth) acrylic acid ester monomer units represented by the formula (4):

-CH ₂ -C (R ³ ) (COOR ⁵ ) - ... (4)

(Meth) acrylic acid ester monomer unit represented by the following formula ( ³⁾ : wherein R ³ is the same as above and R ⁵ represents an alkyl group having 6 or more carbon atoms, is blended with a polyoxyalkylene polymer having a crosslinkable silicon group And the like.

The R ^{4 in the} formula (3) is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group and a t-butyl group, preferably 1 to 4 carbon atoms, An alkyl group having 1 to 2 carbon atoms. The alkyl group for R ⁴ may be used singly or in combination of two or more.

Examples of R ^{5 in the} formula (4) include those having 6 or more carbon atoms such as a 2-ethylhexyl group, a lauryl group and a stearyl group, usually having 7 to 30 carbon atoms, preferably 8 to 20 carbon atoms, Alkyl group. As in the case of R ⁴ , the alkyl group for R ⁵ may be used singly or in combination of two or more.

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

As the (meth) acrylic acid ester-based polymer having a crosslinkable silicon group used in a process for producing an organic polymer in which a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic ester polymer having a crosslinkable silicon group are blended, (Meth) acrylic acid alkyl ester monomer unit having an alkyl group having 1 to 8 carbon atoms and (2) a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having a carbon number of 10 or more (Meth) acrylate-based copolymer containing a (meth) acrylate ester-based copolymer.

The number average molecular weight of the (meth) acrylic acid ester-based polymer is preferably 600 to 10,000, more preferably 600 to 5,000, and further preferably 1,000 to 4,500. When the number average molecular weight is within this range, compatibility with the polyoxyalkylene polymer having a crosslinkable silicon group is improved. The (meth) acrylic acid ester-based polymer may be used alone or in combination of two or more. The blending ratio of the polyoxyalkylene polymer having a crosslinkable silicon group and the (meth) acrylic ester polymer having a crosslinkable silicon group is not particularly limited, but it is preferable that the total amount of the (meth) acrylic ester polymer and the polyoxyalkylene polymer is 100 parts by mass Is preferably within a range of 10 to 60 parts by mass, more preferably within a range of 20 to 50 parts by mass, and still more preferably within a range of 25 to 45 parts by mass, relative to the total amount of the (meth) acrylic ester polymer. When the amount of the (meth) acrylic ester polymer is more than 60 parts by mass, the viscosity is increased and the workability is deteriorated.

In addition, as a production method of an organic polymer obtained by blending a (meth) acrylic acid ester-based copolymer having a crosslinkable silicon group, the (meth) acrylate-based monomer is polymerized in the presence of an organic polymer having a crosslinkable silicon group Method can be used.

[(B) Photobase generator]

The photobase generator (B) acts as a curing catalyst for the organic polymer containing a crosslinkable silicon group when irradiated with light (A). In the photobase generator (B), bases and / or radicals are generated by the action of active energy rays such as ultraviolet rays, electron beams, X-rays, infrared rays and visible rays. (1) a compound which decomposes by nucleophilic substitution reaction or dislocation reaction in the molecule to release amines, or (2) a compound which decomposes by nucleophilic substitution reaction or dislocation reaction in the molecule to form an organic acid and a base salt which are decomposed by decarbonation by irradiation with active energy rays such as ultraviolet rays, visible light, 3) a known photoacid generator (B) such as a compound capable of generating a predetermined chemical reaction by irradiation of an energy ray such as ultraviolet rays, visible light or infrared rays to emit a base. The base generated from the photobase generator (B) has a function of curing the component (A).

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

Examples of the acyclic amidines include guanidine-based compounds and bicyanide-based compounds described in WO2015-088021. Among the acyclic amidine compounds, for example, the photobase generator which generates an aryl-substituted guanidine-based compound or an aryl-substituted anhydride-based compound described in WO2015-088021, when used as a catalyst for the polymer (A) It is preferable that the curing property of the surface shows a tendency to be good and that the adhesiveness of the obtained cured product tends to be good.

The cyclic amidines include, for example, cyclic guanidine compounds, imidazoline compounds, imidazole compounds, tetrahydropyrimidine compounds, triazabicycloalkane compounds, diazabicycloal compounds described in WO2015-088021 Based compounds.

Among the cyclic amidines, 1,8-diazabicyclo [5.4.0] undecene-7 ((meth) acrylate) is preferable because it is industrially easily available, and the pKa value of the conjugated acid is 12 or more, DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN).

As the photobase generator (B), various photobase generators can be used. A photo-latent amine compound that generates an amine compound by the action of an active energy ray is preferred. Examples of the photolatent amine compound include a photolatent primary amine that generates an amine compound having a primary amino group by the action of an active energy ray, an amine compound having a secondary amino group by the action of an active energy ray Photo-potential secondary amines, and photolatent tertiary amines that generate an amine compound having a tertiary amino group by the action of an active energy ray can all be used. In view of the fact that the generated base shows high catalytic activity, a photolatent tertiary amine is more suitable.

Examples of the photolatent primary amine and photolatent secondary amine include ortho nitrobenzyl urethane compounds described in WO2015 / 088021; Dimethoxybenzyl urethane compounds; Benzoin carbamates; o-acyloximes; o-carbamoyl oximes; N-hydroxyimidocarbamates; Formanilide derivatives; Aromatic sulfonamides; Cobalt amine complexes and the like.

Examples of the photolatent tertiary amine include an? -Aminoketone derivative, an? -Ammonium ketone derivative, a benzylamine derivative, a benzylammonium salt derivative, an? -Aminoalkene derivative, an? -Ammonium alkene derivative, Benzyloxycarbonylamine derivatives which generate amidine by light, and salts of carboxylic acids and tertiary amines.

Examples of the? -amino ketone compound include 5-naphthoylmethyl-1,5-diazabicyclo [4.3.0] nonane, 5- (4'-nitro) phenacyl-1,5-diazabicyclo [4.3. Aminoquinone) -1-methyl-1-morpholinoethane (Irgacure 907), 2-benzyl-2-dimethylamino- (4-morpholinophenyl) -butanone (Irgacure 369), 2- (4-methylbenzyl) -2-dimethylamino-1- Aminoketone compounds which generate tertiary amines having a tertiary amine group composed of one nitrogen atom, such as N, N'-tetramethylcyclohexane (Cure 379).

Examples of the? -ammonium ketone derivative include 1-naphthoylmethyl- (1-azonia-4-azabicyclo [2,2,2] -octane) tetraphenylborate, 5- (4'- (5-azonia-1-azabicyclo [4.3.0] -5-nonene) tetraphenylborate.

Examples of the benzylamine derivative include 5-benzyl-1,5-diazabicyclo [4.3.0] nonane, 5- (anthracen-9-ylmethyl) -1,5-diazabicyclo [4.3.0] nonane , And benzylamine derivatives such as 5- (naphtho-2-yl-methyl) -1,5-diazabicyclo [4.3.0] nonane.

Examples of benzylammonium salt derivatives include (9-anthryl) methyl 1-azabicyclo [2.2.2] octanium tetraphenyl borate, 5- (9-anthrylmethyl) -1,5-diazabicyclo [4.3.0 ] -5-nonenetium tetraphenylborate, and the like.

Examples of the? -aminoalkene derivative include 5- (2 '- (2 "-naphthyl) allyl) -1,5-diazabicyclo [4.3.0] nonane.

Examples of the? -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 WO2015-088021.

Examples of the salt of a carboxylic acid and a tertiary amine include an? -Ketocarboxylic acid ammonium salt and a carboxylic acid ammonium salt described in WO2015-088021.

Among the photo-base generators (B), a photo-latent tertiary amine is preferable in that the generated bases exhibit a high catalytic activity, and the base generation efficiency is high and the storage stability as a composition is good. , Benzyl-substituted amine derivatives,? -Aminoketone derivatives and? -Ammonium ketone derivatives are preferable. In particular, the? -Amino ketone derivative and? -Ammonium ketone derivative are more preferable, and the? -Amino ketone derivative is more preferable in view of solubility in the compound because base generation efficiency is better. Among α-amino ketone derivatives, α-amino ketone compounds which generate amidines are preferred from the basic strength of the generated bases, and tertiary amines having tertiary amine groups composed of one nitrogen atom are generated Amino-ketone compounds.

These photobase generators (B) may be used alone or in combination of two or more. The blending ratio of the photo-base generator (B) is not particularly limited, but is preferably from 0.01 to 50 parts by mass, more preferably from 0.1 to 40 parts by mass, further preferably from 0.5 to 0.5 parts by mass, relative to 100 parts by mass of the organic polymer (A) To 30 parts by mass is more preferable.

[(C1) silicon compound having Si-F bond]

(C1) The silicon compound having a Si-F bond functions as a curing catalyst for the organic polymer (A) containing a crosslinkable silicon group. (C1) As the silicon compound having a Si-F bond, various compounds including a silicon group having Si-F bonds (hereinafter occasionally referred to as a fluorosilyl group) can be used, and there is no particular limitation, Both the compound and the polymer compound can be used. Organosilicon compounds having a fluorosilyl group are preferred, and organic polymers having a fluorosilyl group are more suitable because of their high safety. Further, a low-molecular-weight organosilicon compound having a fluorosilyl group is preferred in that the formulation has a low viscosity.

(C1) Examples of the silicon compound having a Si-F bond include the fluorosilanes described in WO2015-088021 represented by the formula (5) and WO2015-088021 shown in the formula (6) (Hereinafter also referred to as a fluorinated compound) and an organic polymer having a fluorosilyl group (hereinafter also referred to as a fluorinated polymer) described in WO2015-088021 can be given as a suitable example.

R ⁶ _{4- d} SiF _d (5)

(In the formula (5), each R ⁶ independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ⁷ SiO- (R ⁷ is each independently a substituted or unsubstituted group having 1 to 20 carbon atoms, A hydrocarbon group or a fluorine atom), d is an integer of 1 to 3, and d is preferably 3. When a plurality of R ⁶ and R ⁷ are present, they are the same It may be good or different.)

-SiF _d R ⁶ _e Z _f ... (6)

(6), R ⁶ and d are the same as in the formula (5), each Z is independently a hydroxyl group or other hydrolyzable group excluding fluorine, e is 0 to 2, f is 0 to 2, and d + e + f is 3. When a plurality of R ⁶ , R ⁷ and Z exist, they may be the same or different.)

Examples of the fluorosilanes represented by the formula (5) include the fluorosilanes represented by the formula (5). Examples thereof include fluorodimethylphenylsilane, vinyltrifluorosilane,? -Methacryloxypropyltrifluorosilane, octadecyltrifluorosilane, and the like.

In the compound having a fluorosilyl group represented by the formula (6), the hydrolyzable group represented by Z is preferably an alkoxy group from the viewpoints of hydrolytic stability and ease of handling, and R ⁶ is preferably a methyl group.

Examples of the fluorosilyl group represented by the formula (6) include a fluorosilyl group in which a silicon group having no hydrolysable group or R ⁶ is a methyl group in addition to fluorine, and a trifluorosilyl group is more preferable.

The compound having a fluorosilyl group represented by the formula (6) is not particularly limited, and both a monomolecular compound and a polymer compound can be used. For example, inorganic silicon compounds; Low molecular weight organosilicon compounds such as vinyldifluoromethoxysilane, vinyltrifluorosilane, phenyldifluoromethoxysilane and phenyltrifluorosilane; And a fluorinated polysiloxane having a fluorosilyl group at the end and represented by the formula (6). Examples of the fluorosilane represented by the formula (5) and the fluorosilane represented by the formula (6) at the end of the main chain or side chain Polymers having a fluorosilyl group are suitable.

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

The fluorinated polymer is a homopolymer homologous to the fluorosilyl group and the main chain skeleton, that is, the number of fluorosilyl groups per molecule, the bonding position thereof, the number of F atoms contained in the fluorosilyl group, and the main chain backbone are homopolymers Or a mixture of plural polymers in which any or all of them are different. All of these fluorinated polymers can be suitably used as a resin component of a curable composition exhibiting fast curability.

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, it tends to be inadequate in terms of the elongation property of the cured product. When the number average molecular weight is more than 100,000, it tends to be inadequate in terms of workability because of high viscosity.

The proportion of the silicon compound (C1) having a Si-F bond is not particularly limited, but when a polymer compound having a number average molecular weight of 3,000 or more such as a fluorinated polymer is used as the component (C1), (A) Is preferably 0.01 to 80 parts by mass, more preferably 0.01 to 30 parts by mass, further preferably 0.05 to 20 parts by mass, per 100 parts by mass of the polymer. A low molecular compound having a fluorosilyl group having a number average molecular weight of less than 3,000 as the component (C1) (for example, a fluorosilane represented by the formula (5) or a low molecular organosilicon compound having a fluorosilyl group represented by the formula (6) A silyl group-containing inorganic silicon compound, etc.) is preferably used in an amount of from 0.01 to 10 parts by mass, more preferably from 0.05 to 5 parts by mass, per 100 parts by mass of the (A) organic polymer containing a crosslinkable silicon group.

The blending ratio of the photo-base generator (B) used as the curing catalyst and the silicon compound (C1) having the Si-F bond is preferably 1: 0.008 to 1: 300 in terms of the mass ratio of (B) :( C1) 1: 0.016 to 1:40 is more preferable.

[(C2) Fluorine-based compound]

Examples of the fluorine-based compound (C2) include at least one fluorine-based compound selected from the group consisting of boron trifluoride, boron trifluoride complex, fluorinating agent and alkali metal salt of polyvalent fluoro compound described in WO2015-088021 have. The fluorine-based compound functions as a compound accelerating the hydrolytic condensation reaction of the crosslinkable silicon group and functions as a curing catalyst for the crosslinkable silicon group-containing organic polymer.

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

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

The photo-curing composition may include at least one member selected from the group consisting of (C1) a silicon compound having a Si-F bond and (C2) a fluorine-based compound. Particularly, in the photo-curing composition according to the present embodiment, when the effect as a composition for post-curing (that is, making into an adhesive) is improved, it is preferable that the composition contains a crosslinkable silicon group- It is preferable to include a compound.

[(D) Multifunctional compound]

(D) a polyfunctional compound having more than one (meth) acryloyl group in more than one molecule, a compound having more than one (meth) acryloyloxy group per molecule or a (meth) acryloyl A compound having an amide group. From the viewpoint of storage stability, a compound having more than one (meth) acryloyloxy group per molecule is preferable. From the viewpoint of reactivity, a compound having more than one (meth) acrylamide group per molecule is preferable.

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

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

Monomers having more than one (meth) acryloyloxy group per molecule are preferably monomers having two or more (meth) acryloyloxy groups per molecule, and examples thereof include polyfunctional (meth) acrylates and the like .

Examples of the polyfunctional acrylates include 1,6-hexadiol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, polypropylene glycol di (Meth) acrylate such as 2,2-bis (4- (meth) acryloxy diethoxyphenyl) propane or 2,2-bis (4- Tri (meth) acrylate monomers such as trimethylolpropane tri (meth) acrylate and tris [(meth) acryloxyethyl] isocyanurate, dimethylol propane tetra (meth) acrylate, pentaerythritol tetra (Meth) acrylate, and tetra-functional or more (meth) acrylate monomers such as pentaerythritol ethoxytetra (meth) acrylate. From the viewpoint of maintaining the flexibility of photo-curable adhesion, a bifunctional (meth) acrylate monomer is preferable and a trifunctional (meth) acrylate monomer and a tetrafunctional or more (meth) acrylate monomer are preferable from the viewpoint of good reactivity .

The polymer having a (meth) acryloyloxy group in more than one molecule per molecule is not particularly limited as long as it is a polymer having an average of more than one (meth) acryloyloxy group per molecule, Meth) acryloyloxy group is preferred.

Examples of the polymer having more than one (meth) acryloyloxy group per molecule include polyether urethane (meth) acrylate (e.g., " UV-3700B ", " UV- UV-2000B "," UV-3000B "," UV-7000B "," KHP-11 "and" KHP-17 "manufactured by Negami Chemical Industries, Ltd.) Acrylate (for example, " RC-300 ", " RC-100C ", manufactured by KANEKA CORPORATION), acrylate (methacrylate) (E.g., " RC-200C "), 1,2-polybutadiene-terminated urethane (meth) acrylate (E.g., "TEAI-1000" manufactured by Nippon Soda Co., Ltd.), 1,4-polybutadiene-terminated urethane (meth) acrylate Site (e. G., Osaka Organic Chemical Co. Preparation "BAC-45") can be given, polyisoprene-terminal (meth) acrylate, bisphenol A epoxy (meth) acrylate and the like.

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

As the compound having more than one (meth) acrylamide group in more than one molecule, a compound having at least two (meth) acrylamide groups in one molecule is preferable, and examples thereof include methylenebisacrylamide, ethylenebisacrylamide, Amide, oxydimethylenebisacrylamide, ethylenedioxybis (N-methyleneacrylamide), and the like.

The mixing ratio of the polyfunctional compound (D) is not particularly limited, but is preferably 0.01 to 100 parts by mass, more preferably 0.1 to 100 parts by mass, and most preferably 0.2 to 100 parts by mass, relative to 100 parts by mass of the (A) The mass part is more preferable. These polyfunctional compounds (D) may be used alone or in combination of two or more.

[(E) a crosslinkable silicon group-containing compound which generates an amino group by light]

The photocurable composition according to the present embodiment may further comprise a crosslinkable silicon group-containing compound which generates at least one amino group selected from the group consisting of a primary amino group and a secondary amino group by (E) light have. A compound containing a crosslinkable silicon group which generates at least one amino group selected from the group consisting of a primary amino group and a secondary amino group by (E) light improves the adhesion performance.

Examples of the crosslinkable silicon group-containing compound that generates at least one amino group selected from the group consisting of a primary amino group and a secondary amino group by light include a compound having a primary amino group and a secondary amino group And any compound capable of generating an aminosilane compound having a crosslinkable silicon group can be used. In the present embodiment, a crosslinkable silicon group-containing compound that produces at least one amino group selected from the group consisting of a primary amino group and a secondary amino group by light is also referred to as a photoaminosilane generating compound.

As the aminosilane compound generated by light irradiation, a compound having a crosslinkable silicon group and a substituted or unsubstituted amino group is used. Examples of the substituent of the substituted amino group include an alkyl group, an aralkyl group and an aryl group. Among these, an alkyl group is preferable from the viewpoint of good adhesiveness. As the crosslinkable silicon group, a silicon-containing group bonded with a hydrolyzable group is preferable. Among them, an alkoxy group such as a methoxy group or an ethoxy group is preferable from the viewpoint of being hydrolyzable and being easy to handle. Of the aminosilane compounds, the hydrolyzable group and the hydroxyl group may be bonded to one silicon atom in a range of 1 to 3, preferably 2 or more, particularly preferably 3.

The aminosilane compound generated by light irradiation is not particularly limited and is preferably an aminosilane compound having a primary amino group (-NH ₂ ) from the viewpoint of adhesiveness, and from the viewpoint of availability,? -Aminopropyltrimethoxy Silane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane and γ- (2-aminoethyl) aminopropyltrimethoxysilane are preferable, and γ-aminopropyltrimethoxy silane Silane, and? -Aminopropyltriethoxysilane are more preferable.

Examples of the optical aminosilane generating compound include a silicon compound having a photofunctional group, an aromatic sulfonamide derivative, an O-acyloxime derivative and a trans-O-cumar derivative represented by the formulas (7) to (8) described in WO2015-088021 Acid derivatives and the like.

In the formula (7), n is an integer of 1 to 3, Y represents a hydroxyl group or a hydrolyzable group, and an alkoxy group is preferable. When there are a plurality of Y, they may be the same or different. R ⁸ represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a substituent, and is preferably a vinyl group, an allyl group, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group. When a plurality of R < ⁸ > exist, they may be the same or different. R ⁹ is a hydrogen atom or an organic group, and is preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a substituent, and more preferably a hydrogen atom. h is an integer of 1 to 5, and j is an integer of 1 to 6. R ¹⁰ is selected from the group consisting of a substituted or unsubstituted hydrocarbon group bonded to the silicon atom and a nitrogen atom at h + j different carbon atoms, and a plurality of substituted or unsubstituted hydrocarbon groups bonded to each other via at least one ether oxygen atom And the molecular weight is 1,000 or less. R ⁹ and R ¹⁰ may combine with each other to form a cyclic structure or may contain a heteroatom bond. Z is an oxygen atom or a sulfur atom, and an oxygen atom is preferred. Q represents an optical functional group.

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

Examples of the photoreactive group Q include known photoreactive groups and are not particularly limited. Examples of the photoreactive group Q include groups having a cyclic structure described in WO2015-088021, oxime residues and substituted groups thereof, and the cyclic structure Is preferred.

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

Examples of the aromatic group include nitrobenzyl groups such as an o-nitrobenzyl group described in WO2015-088021, an m-nitrobenzyl group described in WO2015-088021 and a p-nitrobenzyl group described in WO2015-088021, Nitrobenzyl group and p-nitrobenzyl group are more preferable, o-nitrobenzyl group is particularly preferable, and o-nitrobenzyl group is particularly preferable. desirable. The groups in the photoactive group may be bonded to each other to form a cyclic structure.

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

Examples of the -OQ group in which the photofunctional group Q is an o-nitrobenzyl group include (2-nitrobenzyl) oxy group, (2-nitrobenzyl) oxy group, (3,4-dimethoxy- And nitrobenzyloxy groups such as a period.

Examples of the -OQ group in which the photofunctional group Q is a p-nitrobenzyl group include a (2,4-dinitrobenzyl) oxy group, a (4-nitrobenzyl) Of a nitrobenzyloxy group.

Examples of the -OQ group in which the photofunctional group Q is a benzyl group include a 3,5-dimethoxybenzyloxy group, a [1- (3,5-dimethoxyphenyl) -1-methylethyl] Benzyloxy groups such as a 9-phenanthrylmethyloxy group, a 1-pyrenylmethyloxy group, a 1- (anthraquinon-2-yl) ethyloxy group and a 9-phenylxanthien- have.

Examples of the residue of the formula (7) or (8) from which the ZQ group is removed include 3- (trimethoxysilyl) propylaminocarbonyl group, 3- (triethoxysilyl) propylaminocarbonyl group, 3- (methyldimethoxysilyl) A monoaminocarbonyl group such as a propylaminocarbonyl group and a 3- (methyldiethoxysilyl) propylaminocarbonyl group; Diaminocarbonyl groups such as N- [3- (trimethoxysilyl) propyl] ethylenediaminocarbonyl group and N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediaminocarbonyl group; And an aminocarbonyl group such as a triaminocarbonyl group such as N- [3- (trimethoxysilyl) propyl] diethylenetriaminocarbonyl group.

Among the aminocarbonyl groups, an aminocarbonyl group having an amino group (-NH ₂ ) from the viewpoint of adhesiveness is preferable, and an aminocarbonyl group having 3- (trimethoxysilyl) propylaminocarbonyl group, 3- (triethoxysilyl) (Trimethoxysilyl) propylaminocarbonyl group is more preferable, and in terms of adhesiveness and curability, 3- (trimethoxysilyl) propylaminocarbonyl group and 3- ( Triethoxysilyl) propylaminocarbonyl group is most preferable.

The compounding ratio of the optical aminosilane-generating compound is not particularly limited, but is preferably from 0.01 to 50 parts by mass, more preferably from 0.1 to 30 parts by mass, and most preferably from 0.1 to 20 parts by mass, relative to 100 parts by mass of the (A) The mass part is more preferable. These optical aminosilane generating compounds may be used alone or in combination of two or more.

[(F) Mono-functional compound having photopolymerizable unsaturated group]

The photocurable composition according to the present embodiment preferably further comprises (F) a monofunctional compound having a photopolymerizable unsaturated group. The viscosity of the photo-curable compound can be lowered by the monofunctional compound (F). As the monofunctional compound (F) having a photopolymerizable unsaturated group, a monofunctional compound having various photopolymerizable unsaturated groups can be used, and there is no particular limitation. For example, a compound having one (meth) acryloyl group in one molecule, And an N-vinyl compound in which a vinyl group is directly bonded to a nitrogen atom.

Examples of the compound having one (meth) acryloyl group in one molecule include a compound having one (meth) acryloyloxy group in one molecule and a compound having one (meth) acrylamide group in one molecule , And a compound having one (meth) acryloyloxy group in one molecule from the viewpoint of storage stability. From the viewpoint of reactivity, a compound having one (meth) acrylamide group in one molecule is preferable.

As the compound having one (meth) acryloyloxy group in one molecule, monomers, oligomers and polymers can all be used. From the viewpoint of viscosity, a monomer having a (meth) acryloyloxy group is preferable. From the viewpoint of the curability, an oligomer having a (meth) acryloyloxy group is suitable.

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

Examples of monofunctional (meth) acrylates include (meth) acrylates having a hydroxyl group such as 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hexaethylene glycol mono 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, dicyclopentenyloxyethyl (meth) acrylate and the like. 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 And long-chain hydrocarbon-based (meth) acrylates having 8 to 18 carbon atoms are preferable from the viewpoint of availability. 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 and the like. Further, N- (meth) acryloyloxyethylhexahydrophthalimide and the like can be given. Examples of the (meth) acrylate having a crosslinkable silicon group include 3- (trimethoxysilyl) propyl (meth) acrylate and the like. When flexibility is required, it is preferable to use monofunctional (meth) acrylates.

As the oligomer having one (meth) acryloyloxy group in one molecule, a polymer having one (meth) acryloyloxy group can be used. For example, an acrylic polymer having a skeleton of an acrylic polymer having one (meth) acryloyloxy group, a urethane (meth) acrylate polymer, a polyester (meth) acrylate polymer, a polyether (meth) , Epoxy (meth) acrylate polymers, and the like.

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

Examples of the N-vinyl compound include N-vinylpyrrolidone and N-vinylcaprolactam. In the present embodiment, the N-vinyl compound is preferable in view of its reactivity and oxygen hardness.

The blending ratio of the (F) monofunctional compound is not particularly limited, but is preferably 0.01 to 100 parts by mass, more preferably 0.1 to 100 parts by mass, further preferably 1 to 100 parts by mass, relative to 100 parts by mass of the (A) More preferably 100 parts by mass. These monofunctional compounds (F) may be used alone or in combination of two or more.

[(G) Adhesion-imparting resin]

The photocurable composition according to the present embodiment preferably further comprises a (G) tackifier resin. (G) The tackifier resin is not particularly limited, and commonly used resins may be mentioned. Specific examples include terpene resins, aromatic modified terpene resins, hydrogenated terpene resins obtained by hydrogenating them, terpene-phenol resins, phenol resins, modified phenol resins, xylene resins, xylene-phenol resins, (Such as cyclopentadiene resin, cyclopentadiene-phenol resin, coumarone resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin C9 hydrocarbon resins, C5 and C9 hydrocarbon copolymer resins, C5 and C9 hydrocarbons and phenol copolymer resins), and hydrogenated petroleum resins. These may be used alone or in combination of two or more.

When the tackifier resin is used for an adherend having a low polarity, it is preferable to use a tackifier resin having a low polarity. When the adherend is used for an adherend having a high polarity, it is preferable to use a tackifier resin having a high polarity. When a tackifier resin is used for a wide adherend from an adherend having a high polarity to an adherend having a low polarity, it is preferable to use a mixture of a tackifier resin having a low polarity and a tackifier resin having a high polarity.

The blending ratio of the (G) tackifier resin is not particularly limited, but is preferably 0.1 to 100 parts by mass, more preferably 1 to 80 parts by mass, per 100 parts by mass of the (A) the organic polymer having a crosslinkable silicon group. These tackifier resins may be used alone or in combination of two or more.

[Other additives]

The blend according to the present embodiment may contain, if necessary, a compound having a (meth) acrylamide group, a compound having an epoxy group, a silane coupling agent, a basic proliferation type aminosilane, a photo radical polymerization initiator, a photosensitizer, An antioxidant, an antioxidant, an ultraviolet absorber, a solvent, a flavoring agent, a pigment, a dye, a conductive powder, a thermally conductive powder, a colorant, a flame retardant, A phosphor, a wax, a resin filler, and the like.

Examples of the compound having an N-methyl (meth) acrylamide group include N-methyl (meth) acrylamide and N- (meth) acryloylmorpholine. The compound having a good balance of curability, , Acryloylmorpholine is preferred.

Examples of the compound having an epoxy group include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, novolak epoxy resin, aliphatic cyclic epoxy resin, brominated epoxy resin, rubber modified epoxy A styrene-butadiene-styrene copolymer, a resin, a urethane-modified epoxy resin, a glycidyl ester compound, an epoxidized polybutadiene, and an epoxidized SBS (SBS indicates a styrene-butadiene-styrene copolymer). When a compound having an epoxy group is further added to the compound according to the present embodiment, the compound according to the present embodiment exhibits high adhesiveness and durability after curing, and is particularly effective for an adherend having an aromatic ring. Further, the use of the optical aminosilane-generating compound or the aminosilane compound is more effective in improving the adhesiveness.

The blend according to the present embodiment can improve the adhesion to an overall adherend such as metal, plastic, and glass by incorporating a silane coupling agent.

Examples of the silane coupling agent include amino group-containing silanes; Ketimine type silanes; Epoxy group-containing silanes; Mercapto group-containing silanes; Vinyl-type unsaturated group-containing silanes; Chlorine atom-containing silanes; Isocyanate-containing silanes; Alkylsilanes; Phenyl group-containing silanes; Isocyanurate group-containing silanes, and the like, but the present invention is not limited thereto. The modified amino group-containing silane in which an amino group is modified by reacting an amino group-containing silane with an epoxy group-containing compound, an isocyanate group-containing compound or a (meth) acryloyl group-containing compound containing the silane group may also be used.

In addition, a silane coupling agent may be added for the purpose of crosslinking the tackifying resin and the organic polymer containing a crosslinkable silicon group. In the case of using a tackifier resin containing phenol or carboxylic acid, for example, by adding an epoxy silane, the crosslinkable silicon group-containing organic polymer and the tackifier resin can be crosslinked to improve the adhesion (adhesion) , It is possible to suppress the change in the adhesive force (adhesive force) due to the continuous movement of the tackifier resin.

The blending ratio of the silane coupling agent is not particularly limited, but is preferably from 0.2 to 20 parts by mass, more preferably from 0.3 to 15 parts by mass, further preferably from 0.5 to 10 parts by mass, per 100 parts by mass of (A) the organic polymer having a crosslinkable silicon group More preferable. These silane coupling agents may be used alone or in combination of two or more.

The compound according to the present embodiment may further contain base-propagating aminosilane for the purpose of improving the adhesive performance. Examples of the basic proliferation type aminosilane include a compound having a basic proliferation type amine compound and a crosslinking silicon group in the amine residue (a compound which produces an amine compound having a crosslinkable silicon group upon decomposition). Examples of such compounds include 9-fluorenylmethyl esters of carbamic acid having a crosslinkable silicon group (C ₁₃ H ₉ CH ₂ OCONR ¹³ R ^{14 wherein} R ¹³ and R ¹⁴ are organic groups such as a hydrogen atom or a hydrocarbon group , At least one of R ¹³ and R ¹⁴ is an organic group such as a hydrocarbon group having a crosslinkable silicon group, a 2-arylsulfonylethyl ester of a carbamic acid having a crosslinkable silicon group (ArSO ₂ CH ₂ CH ₂ OCONR ¹³ R ¹⁴ , wherein Ar is an aromatic group which may have a substituent, R ¹³ and R ¹⁴ are as defined above), 3-nitropentan-2-yl ester of carbamic acid having a crosslinkable silicon group (CH ₃ CH ₂ CH (NO ₂ ) CH (CH ₃ ) OCONR ¹³ R ¹⁴ , wherein R ¹³ and R ¹⁴ are as defined above.

Examples of the photo radical polymerization initiator include arylalkyl ketones such as benzoin ether derivatives and acetophenone derivatives, oxime ketones, acylphosphine oxides, thiobenzoic acid S-phenyls, titanocenes, and derivatives obtained by high- .

The formulation according to the present embodiment may further contain a diluent. By mixing a diluent, physical properties such as viscosity can be adjusted. As the diluting agent, various diluents can be used, and there is no particular limitation. Examples thereof include saturated hydrocarbon solvents such as normal paraffin and isoparaffin, alpha -olefin derivatives such as HS dimmer (trade name, manufactured by Hokoku Kogyo Co., Ltd.), aromatic hydrocarbon solvents, alcohol solvents such as diacetone alcohol, ester solvents, acetyl citrate And various solvents such as citric acid ester-based solvents such as triethyl, ketone-based solvents and the like.

There is no particular limitation on the flash point of the diluent. However, considering the safety of the compound according to the present embodiment, it is preferable that the flash point of the compound according to the present embodiment is high and the volatile substance from the compound according to the present embodiment is low . Therefore, the flash point of the diluent is preferably 60 DEG C or higher, more preferably 70 DEG C or higher. When two or more kinds of diluents are mixed, it is preferable that the mixed diluent has a flash point of 70 ° C or higher. In general, the diluent having a high flash point tends to have a low dilution effect with respect to the blend according to the present embodiment, and therefore, it is preferable that the flash point is 250 캜 or lower.

Considering both safety and dilution effect of the formulation according to the present embodiment, a diluent is preferably a saturated hydrocarbon solvent, and normal paraffin and isoparaffin are more suitable. Normal paraffins and isoparaffins preferably have 10 to 16 carbon atoms, and more preferably 14 to 16 carbon atoms in the effect on the environment (VOC).

The blending ratio of the diluting agent is not particularly limited, but from the viewpoint of improvement of the coating workability by the blending and lowering of the physical properties, it is preferable to blend 0 to 25% of the diluent with respect to the unit weight of the blend according to the present embodiment, More preferably from 0.1 to 15%, and even more preferably from 1 to 7%. The diluent may be used alone or in combination of two or more.

As the resin filler, a particle type filler made of an organic resin or the like can be used. For example, as the resin filler, organic fine particles such as an ethyl acrylate resin, a polyurethane resin, a polyethylene resin, a polypropylene resin, a urea resin, a melamine resin, a benzoguanamine resin, a phenol resin, an acrylic resin and a styrene resin can be used.

The resin filler (resin fine powder) is preferably a spheric type easily obtained by suspension polymerization of a monomer (e.g., methyl methacrylate) or the like. Further, since the resin filler is suitably contained as a filler in the solution composition, a spherical crosslinked resin filler is preferable.

The resin filler is preferably a urethane resin filler or an acrylic resin filler, and more preferably a urethane resin filler, from the viewpoint of good compatibility with the formulation according to the present embodiment.

The average particle diameter of the resin filler is preferably 1 to 150 mu m, more preferably 5 to 30 mu m. In the present embodiment, the average particle diameter is a 50% cumulative particle diameter measured by a laser diffraction scattering method. If the average particle diameter is smaller than 1 占 퐉, the conductive adhesive agent may be difficult to disperse in the system. Further, when it is larger than 150 탆, it tends to be easily clogged in the nozzle of the application.

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

When the blend according to the present embodiment is used for applications requiring light shielding properties, it is preferable that the resin filler includes a black resin filler. By using a black resin filler having an average particle size of 1 to 150 占 퐉, it is possible to obtain good deep-part curability even when a single-wavelength LED lamp or the like is used, and excellent light shielding and deep curability can be achieved.

The method for producing the photo-curing composition is not particularly limited, and can be produced, for example, by blending predetermined amounts of the components (A) to (D), blending other compounding materials as required, and degassing and stirring. The mixing order of each component and other compounding materials is not particularly limited and can be appropriately determined.

The photo-curable composition may be of a one-component type or a two-component type, if necessary, but may be suitably used as a one-component type. The photo-curable composition according to the present embodiment is a photo-curable composition which is cured by light irradiation and can be cured at room temperature (for example, 23 ° C) and is suitably used as a room temperature curable curable composition. Thereby accelerating the curing.

The method for producing a cured product according to the present embodiment is a method for forming a cured product by irradiating light to the photo-curable composition according to the present embodiment. The cured product according to the present embodiment is a cured product obtained by this method.

The manufacturing method of the product according to the present embodiment is a method of manufacturing using the photo-curing composition according to the present embodiment. The product according to the present embodiment is an article produced by using this method and can be suitably used for various products such as electronic circuits, electronic parts, building materials, and automobiles.

With respect to the photo-curable composition according to the present embodiment, the conditions for irradiating light are not particularly limited. When the active energy ray is irradiated at the time of curing, the active energy ray is irradiated with ultraviolet rays, visible rays, Electron beams such as X-rays and? -Rays, electron beams, proton beams, neutron beams, and the like can be used. Curing by irradiation with ultraviolet rays or electron beams is preferable, and curing by irradiation of ultraviolet rays is more preferable in terms of curing speed, ease of access to the irradiation apparatus, price, easiness of handling under sunlight or general illumination, and the like. The ultraviolet rays include g-line (wavelength 436 nm), h-line (wavelength 405 nm), and i-line (wavelength 365 nm). Examples of the active energy source include, but are not limited to, high-pressure mercury lamps, low-pressure mercury lamps, electron beam irradiators, halogen lamps, light emitting diodes, semiconductor lasers and metal halides depending on the properties of the photo- Diodes are preferred.

The irradiation energy is preferably 10 to 20,000 mJ / cm2, more preferably 20 to 10,000 mJ / cm2, and even more preferably 50 to 5,000 mJ / cm2 in the case of ultraviolet rays. If it is less than 10 mJ / cm < 2 >, the curability may be insufficient, and if it is larger than 20,000 mJ / cm < 2 >, the light irradiation more than necessary may waste time and cost and damage the substrate.

The method of applying the photocurable composition according to the present embodiment to the adherend is not particularly limited, but application methods such as screen printing, stencil printing, roll printing, dispenser application, jet dispenser application, spray application, do.

Further, in the present embodiment, there is no limitation on the timing of application and light irradiation of the photocurable composition to an adherend. For example, the photo-curable composition can be irradiated with light and then bonded to an adherend to produce a product. Further, the photocurable composition can be applied to an adherend and irradiated with light, whereby the composition can be cured to produce a product.

The photo-curable composition according to the present embodiment is a fast curing photo-curable composition having excellent workability and is particularly useful as a point-and-stick composition, and is useful as an adhesive or a sealant, an adhesive material, a coating material, a potting material, Gaskets, and the like. The photo-curing composition according to the present embodiment is useful as a coating agent used for, for example, a coating for the purpose of moisture-proofing or insulation of a mounting circuit board or the like, a coating of the outer periphery of a panel or a panel of solar power generation, Sealing materials for building and industrial use such as sealing materials for double-layer glass, and automotive sealing materials; Electrical and electronic parts such as encapsulant for solar cells; Electrical insulation materials such as insulating coverings for wires and cables; A material for forming a stereolithography by an optical shaping method; adhesive; glue; Elastic adhesive; Contact adhesive; Applications requiring rework or repair; Liquid gaskets, and the like.

The liquid gasket can be used, for example, for Formed In Place Gasket (FIPG) for electronic devices. That is, the photo-curing composition according to the present embodiment is in a liquid state before curing. Therefore, the photocurable composition according to the present embodiment is a FIPG for electronic equipment, and even if exposed to air, it is not cured before the active energy ray irradiation, so that a sufficient working time can be secured. It can be used as a liquid gasket for an electronic device product which is cured in a short time while being sufficiently present.

In the case of the housing member joined using the liquid gasket made of the photo-curable composition according to the present embodiment, when the housing member is fitted after the active energy ray irradiation, the photo-curing composition The liquid-phase gasket formed by using does not come out, and the housing member can be removed with a small force. Further, the removal of the housing member is not limited to the initial stage of curing, and the housing member can be removed with a small force even after curing. Then, after the housing member is removed, the housing member can be rejoined using the liquid gasket as it is, and the sealing performance such as the original waterproof performance can be maintained even after the re-combination. However, by additionally adding an optical aminosilane generating compound or an aminosilane compound, it is possible to design such that it can not be removed after a certain period of time even though it can be removed within a certain period of time.

The liquid gasket made of the photo-curing composition according to the present embodiment can be used after coating one or both of a plurality of housing members such as a main body and a cover to be sealed, irradiating active energy rays, and then combining the housing members . Since the organic polymer containing a crosslinkable silicon group is cured by the moisture in the air after irradiation with the active energy ray, curing proceeds when the housing member is left after the curing. When the curing speed is increased, it may be heated.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. These embodiments are illustrative and should not be construed as limiting.

1) Measurement of the number average molecular weight

The number average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions. In the description of the examples, the molecular weight at maximum frequency measured by GPC under the following measurement conditions and converted to standard polyethylene is referred to as a number average molecular weight.

Analysis apparatus: Alliance (manufactured by Waters Corporation), 2410 type differential refraction detector (manufactured by Waters), 996 type multi-wavelength detector (manufactured by Waters), Milleniam data processing apparatus (manufactured by Waters)

Column: Plgel GUARD + 5 占 퐉 Mixed-C 占 3 (50 占 7.5 mm, 300 占 7.5 mm: manufactured by PolymerLab Co.)

ㆍ Flow rate: 1 mL / min

ㆍ Converted polymer: Polyethylene

ㆍ Measuring temperature: 40 ℃

Solvent in GPC measurement: THF

2) Measurement of NMR and IR

NMR and IR were measured using the following measuring apparatus.

FT-NMR measurement apparatus: JNM-ECA500 (500 MHz) manufactured by Nihon Denshi Co.,

FT-IR measuring apparatus: FT-IR460Plus manufactured by Nihon Bunko Co., Ltd.

(Synthesis Example 1) Synthesis of polyoxyalkylene polymer A1 having a trimethoxysilyl group at the terminal

Propylene oxide was reacted with ethylene glycol as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst to obtain a polyoxypropylene diol. A polyoxyalkylene polymer having an allyl group at the terminal of the obtained polyoxypropylene diol was obtained in accordance with the method of Synthesis Example 2 of WO2015-088021. The polyoxyalkylene polymer having an allyl group at the terminal thereof was reacted with a hydrogenated silicon compound, trimethoxysilane, by adding a platinum vinylsiloxane complex isopropanol solution to obtain a polyoxyalkylene polymer A1 having a trimethoxysilyl group at its terminal .

The molecular weight of the resulting polyoxyalkylene polymer A1 having a trimethoxysilyl group at the terminal thereof was measured by GPC, and as a result, the peak top molecular weight was 25,000 and the molecular weight distribution was 1.3. ^{By 1} H-NMR measurement, the terminal trimethoxysilyl group was 1.7 per one molecule.

(Synthesis Example 2) Synthesis of polyoxyalkylene polymer A2 having a trimethoxysilyl group at the terminal

Propylene oxide was reacted with ethylene glycol as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst to obtain a polyoxypropylene diol. A polyoxyalkylene polymer having an allyl group at the terminal of the obtained polyoxypropylene diol was obtained in accordance with the method of Synthesis Example 2 of WO2015-088021. The polyoxyalkylene polymer having an allyl group at the terminal thereof was reacted with a hydrogenated silicon compound, trimethoxysilane, by adding a platinum vinylsiloxane complex isopropanol solution to obtain a polyoxyalkylene polymer A2 having a trimethoxysilyl group at its terminal .

The molecular weight of the obtained polyoxyalkylene polymer A2 having a trimethoxysilyl group at the terminal thereof was measured by GPC, and as a result, the peak top molecular weight was 12,000 and the molecular weight distribution was 1.3. ^{By 1} H-NMR measurement, the terminal trimethoxysilyl group was 1.7 per one 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, 0.10 g of titanocene diclcide as a metal catalyst, 8.60 g of 3-mercaptopropyltrimethoxysilane (Meth) acryl-based polymer A3 having a trimethoxysilyl group was obtained by using 20.00 g of a benzoquinone solution (95% THF solution) as a polymerization terminator in accordance with the method of Synthesis Example 4 of WO2015-088021. (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 in the molecule by the ¹ H-NMR measurement was 2.00 per molecule.

(Synthesis Example 4) Synthesis of fluorinated polymer C1-1

A polyoxypropylene diol having a molecular weight of 14,500 and a molecular weight distribution of 1.3 was obtained by reacting propylene oxide with a polyoxypropylene diol having a molecular weight of about 2,000 as an initiator in the presence of a zinc hexacyanocobaltate- . A polyoxyalkylene polymer having an allyl group at the terminal of the obtained polyoxypropylene diol was obtained in accordance with the method of Synthesis Example 2 of WO2015-088021. Methyldiethoxysilane, which is a hydrogenated silicon compound, was added to a polyoxyalkylene polymer having an allyl group at the terminal thereof, followed by reaction with a platinum vinylsiloxane complex isopropanol solution to obtain a polyoxyalkylene polymer A4 having a methyldimethoxysilyl group at the terminal thereof . The molecular weight of the obtained polyoxyalkylene polymer A4 having a methyldimethoxysilyl group at the terminal thereof was measured by GPC, and as a result, the peak top molecular weight was 15,000 and the molecular weight distribution was 1.3. ^{According to 1} H-NMR measurement, the methyldimethoxysilyl group at the terminal was 1.7 per one molecule.

Subsequently, by using 2.4 g of a BF ₃ diethyl ether complex, 1.6 g of dehydrated methanol, 100 g of Polymer A4, and 5 g of toluene, a poly (methyl methacrylate) having a fluorosilyl group at the terminal was synthesized in accordance with the method of Synthesis Example 4 of WO2015-088021. To obtain an oxyalkylene-based polymer C1-1 (hereinafter referred to as fluorinated polymer C1-1). The ¹ H-NMR spectrum (measured by NMR 400 manufactured by Shimazu Co., Ltd.) of the obtained fluorinated polymer C1-1 was measured in a CDCl ₃ solvent. As a result, it was found that the ratio of the silyl methylene (-CH ₂ -Si) The peak (m, 0.63 ppm) was lost and the broad peak appeared on the long side of the author (0.7 ppm).

(Synthesis Example 5) Synthesis of crosslinkable silicon group-containing compound E1 which generates an amino group by light

15.3 parts of 2-nitrobenzyl alcohol and 344 parts of toluene were added to the flask, and the mixture was refluxed at about 113 DEG C for 60 minutes. Thereafter, 20.5 parts of 3-isocyanatopropyltrimethoxysilane was added dropwise and stirred for 5 hours to obtain a compound (a crosslinkable silicon group-containing compound which produces an amino group by the light represented by the following formula (9) Referred to as compound E1). As a result of the IR spectrum measurement of the optical aminosilane generating compound E1, -N = C = O bond was not detected.

(Synthesis Example 6)

589.4 parts by weight of polypropylene glycol (trade name: Diol-2000, manufactured by Mitsui Chemicals Polyurethanes Ltd.) was dehydrated and then 110.6 parts by weight of 4,4-diphenylmethane diisocyanate (MDI) was added to the stirrer equipped with a thermometer And the mixture was reacted at 70 to 90 캜 for 3 hours under a nitrogen gas stream to obtain a urethane prepolymer A having an NCO / OH equivalent ratio of 1.5. 0.5 equivalent of 3-mercaptopropyltrimethoxysilane was reacted with the urethane prepolymer A with respect to the NCO group of the urethane prepolymer A, and a polymer having an NCO group at the other terminal of the trimethoxysilyl group at one end was obtained by averaging . An equivalent amount of 4-hydroxybutyl acrylate was reacted with the polymer to obtain NCO groups of the obtained polymer, and a polymer A4 having a trimethoxysilyl group at one end and an acryloyloxy group at the other end was obtained on average.

(Examples 1 to 12 and Comparative Examples 1 to 7)

Each of the compounding materials was added at the compounding ratios shown in Table 1, and the mixture was mixed and stirred to prepare a photocurable composition.

[Table 1]

In Table 1, the blending amounts of the respective compounding materials are shown in g, the polyoxyalkylene polymers A1 and A2 are the polyoxyalkylene polymers A1 and A2 obtained in Synthesis Examples 1 and 2, and the acrylic polymer A3 is the polyoxyalkylene polymers A1 and A2 obtained in Synthesis Example 3 The organic polymer A4 having the crosslinkable silicon group and the photo radical polymerizable vinyl group in the molecule is the polymer A4 obtained in Synthesis Example 6, the fluorinated polymer C1-1 is the fluorinated polymer C1-1 obtained in Synthesis Example 4, The aminosilane generating compound E1 is the optical aminosilane generating compound E1 obtained in Synthesis Example 5, and the other compounding materials are as follows.

* 1) Photobase generator B1: Irgacure (registered trademark) 379EG [trade name, manufactured by BASF, 2- (dimethylamino) -2 - [(4- methylphenyl) methyl] Phenyl) -1-butanone] in 70% PC (propylene carbonate).

* 2) Photobase generator B2: 5% PC solution of SA-2 (trade name of SANA PRO).

* 3) Multifunctional compound D1: 1,6-hexanediol diacrylate, trade name "SR238NS" (manufactured by Sato M GmbH), bifunctional acrylate monomer.

* 4) Multifunctional compound D2: trimethylol propane, trade name "Light Acrylate TMP-A" (manufactured by Kyoei Chemical Industry Co., Ltd.), trifunctional acrylate monomer.

* 5) Multifunctional compound D3: dipentaerythritol hexaacrylate, trade name "Light Acrylate DPE-6A" (manufactured by Kyoei Chemical Co., Ltd.), 6-functional acrylate monomer.

* 6) Multifunctional compound D4: Urethane acrylate, trade name "NK Oligo U-15HA" (manufactured by Shin-Nakamura Chemical Co., Ltd.), and polymer having 15 acryloyloxy groups.

* 7) Polyfunctional compound D5: Acrylic acrylate, trade name "RC100C" (manufactured by Kaneka), polymer having two acryloyloxy groups.

* 8) Mono-functional compound F1: methoxydipropylene glycol acrylate, trade name "Light Acrylate DPM-A" (manufactured by Kyoei Iseki Chemical Co., Ltd.), monofunctional acrylate.

* 9) Monofunctional compound F2: phenoxyethyl acrylate, trade name "Light Acrylate PO-A" (manufactured by Kyoei Iseki Chemical Co., Ltd.).

* 10) Adhesion-imparting resin G1: "Fine Crystal KE-100" (manufactured by Arakawa Chemical Industries, Ltd.).

* 11) Compound having an epoxy group: bisphenol A type epoxy resin, trade name "JER828" (Mitsubishi Resin Co., Ltd.).

* 12) Opened type photo radical generator: Irgacure (registered trademark) 1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one manufactured by BASF)

* 13) Tin catalyst: 33% PC solution of Neostan U-100 (trade name, manufactured by Nitto Chemical Industry Co., Ltd.).

The obtained photocurable composition was subjected to creep test and tensile shear bond strength test by the following method. The results are shown in Table 1.

1) Creep test

The resulting photocurable composition was applied to an adherend material (acrylic resin) having an area of 5 mm x 25 mm and a thickness of 100 mu m and irradiated with UV light (irradiation condition: UV-LED lamp (wavelength 365 nm, illuminance 1000 mW / cm 2) : 3000 mJ / cm < 2 >]. After the irradiation, the adherend material (acrylic resin) was immediately adhered, pressed by a bulldog clip (small), cured for 30 seconds under an environment of 23 ° C and 50% RH in a dark room and then subjected to a creep test (weight: 10 g) And evaluated by evaluation criteria.

O: The adherend did not fall down, X: The adherend fell.

2) Tensile shear bond strength test

(Irradiation condition: UV-LED lamp (wavelength: 365 nm, illuminance: 1000 mW / cm 2), cumulative light quantity: 3000 mJ / cm 2) was applied to the adherend [acrylic resin] so that the obtained photo- did. Immediately after the irradiation, the adherend material (acrylic resin) was adhered to an area of 25 mm × 25 mm, pressed by bulldog clips (small), and cured for 3 hours under an environment of 23 ° C. and 50% RH in a dark room. After curing, the test was carried out at a test speed of 50 mm / min in accordance with the tensile shear bond strength test method of JIS K6850 rigid adherend. The results are shown in Table 1.

As can be seen from Table 1, all of the photocurable compositions according to Examples 1 to 12 showed good creep test and sufficient tensile shear bond strength.

(Examples 13 to 15 and Comparative Examples 8 to 11)

Each of the compounding materials was added at the mixing ratios shown in Table 2 and mixed and stirred to prepare a photo-curable composition for a liquid gasket.

[Table 2]

In Table 2, the compounding amounts of the respective compounding materials are expressed in g, the polyoxyalkylene polymers A1 and A2 are the polyoxyalkylene polymers A1 and A2 obtained in Synthesis Examples 1 and 2, and the acrylic polymer A3 is the polyoxyalkylene polymers A1 and A2 obtained in Synthesis Example 3 Acryl polymer A3, and the fluorinated polymer C1-1 is the fluorinated polymer C1-1 obtained in Synthesis Example 4. The compounds having the same tin as those in Table 1 represent the same compounds as in Table 1. Details of other compounding materials are as follows.

* 14) Photobase generator B3: Irgacure (registered trademark) 379EG (BASF, 2- (dimethylamino) -2 - [(4- methylphenyl) methyl] -1- [4- (4-morpholinyl) Phenyl] -1-butanone), and diluted to 50 mass% with propylene carbonate solution. In Table 2, the mass part of the solid content is described.)

* 15) Multifunctional compound D6: Wright acrylate DPM-A (trade name, methoxydipropylene glycol acrylate, manufactured by Kyoei Chemical Industry Co., Ltd.)

* 16) Multifunctional compound D7: UV3700B (produced by Nihon Kogyo Seiyaku K.K., a urethane acrylate, a polymer having two acryloyloxy groups)

* 17 Anti-sagging agent: AEROSIL (registered trademark) R972 (hydrophobic silica, manufactured by Aero Chemical Co., Ltd.)

The obtained liquid phase gasket was tested by the following method. The results are shown in Table 2.

(Workability test at non-UV irradiation)

(Hereinafter referred to as " dispenser robot A ") equipped with a needle having an inner diameter of 0.84 mm as a discharging needle under the condition of 23 ° C and 50% RH under a fluorescent lamp to which a film for cutting a wavelength of 500 nm or less was adhered , The workability of the composition prepared in Example 13 at the time of non-UV irradiation was tested. Under the environment of 23 占 폚 and 50% RH, the PET film was continuously applied, and contact with the fingers was performed to measure the time at which dispensing was possible.

, &Quot; ", " ", " ", " x ", "

(Shape retention)

The photocurable composition was coated on the periphery of a glass plate having a length of 75.00 mm, a length of 25.00 mm and a thickness of 2.00 mm using a dispenser robot A with a square (line width of 1 mm) having a length of 65.00 mm and a width of 18.00 mm. : A UV-LED lamp (wavelength 365 nm, illuminance: 1000 mW / cm 2), cumulative light quantity: 1000 mJ / cm 2, hereinafter referred to as "irradiation condition 1". Immediately after the irradiation, another one of the same size glass plates was bonded. Thereafter, 500 g of weight was placed under an environment of 23 ° C and 50% RH, and cured for 15 minutes. After curing, the width was evaluated as "? &Quot; when the width of the curable composition before bonding was less than 2 times, "? &Quot;

(Initial waterproof property)

The photo-curing composition was coated on the periphery of a glass plate having a length of 75.00 mm, a length of 25.00 mm and a thickness of 2.00 mm using a dispenser robot A with a square (line width of 1 mm) having a length of 65.00 mm and a width of 18.00 mm. Is the irradiation condition 1). Immediately after the irradiation, another one of the same size glass plates was bonded. Thereafter, 500 g of weight was placed under an environment of 23 ° C and 50% RH, and cured for 15 minutes. After curing, the glass plate laminated to each other in a water depth of 1.0 m was allowed to settle for 30 minutes, and the presence of water intrusion into the inside of the gasket was visually determined. &Quot; when there was no intrusion of water, and " x " when there was intrusion of water. In addition, Comparative Example 8 hardened to a state where bonding was impossible, and Comparative Examples 10 and 11 could not be evaluated because they were uncured.

(Initial peelability)

The photo-curing composition was coated on the periphery of a glass plate having a length of 75.00 mm, a length of 25.00 mm and a thickness of 2.00 mm using a dispenser robot A with a square (line width of 1 mm) having a length of 65.00 mm and a width of 18.00 mm. Is the irradiation condition 1). Immediately after the irradiation, another one of the same size glass plates was bonded. Thereafter, 500 g of weight was placed under an environment of 23 ° C and 50% RH, and cured for 1 minute. After curing, the glass plates laminated to each other were peeled off and fractured between the glass and the adhesive. The fracture at the interface of the glass plate was evaluated as "? &Quot;, and the cohesive failure of the adhesive was evaluated as " x ". In addition, Comparative Example 8 was cured to a state in which bonding was impossible, and Comparative Examples 9 to 11 were uncured and could not be evaluated.

(Waterproof property of the peeled liquid gasket)

The photo-curing composition was coated on the periphery of a glass plate having a length of 75.00 mm, a length of 25.00 mm and a thickness of 2.00 mm using a dispenser robot A with a square (line width of 1 mm) having a length of 65.00 mm and a width of 18.00 mm. Is the irradiation condition 1). Immediately after the irradiation, another one of the same size glass plates was bonded and cured for 1 minute. Thereafter, the glass plates laminated and bonded to each other were peeled off once and joined again. After re-bonding, 500 g of weight was placed under an environment of 23 ° C and 50% RH and cured for 15 minutes. After curing, the glass plate laminated to each other in a water depth of 1.0 m was allowed to settle for 30 minutes, and the presence of water intrusion into the inside of the gasket was visually determined. &Quot; when there was no intrusion of water, and " x " when there was intrusion of water. Comparative Example 8 was cured to a state in which bonding was impossible, and Comparative Examples 9 to 11 were uncured after curing for 1 minute, and evaluation was not performed because they could not be cleanly peeled off from both glass plates.

(Peelability after curing)

The photo-curing composition was coated on the periphery of a glass plate having a length of 75.00 mm, a length of 25.00 mm and a thickness of 2.00 mm using a dispenser robot A with a square (line width of 1 mm) having a length of 65.00 mm and a width of 18.00 mm. Is the irradiation condition 1). Immediately after the irradiation, another one of the same size glass plates was bonded. Thereafter, 500 g of weight was placed under an environment of 23 ° C and 50% RH, and cured for one day. After curing, the glass plates laminated to each other were peeled off and fractured between the glass and the adhesive. The fracture at the interface of the glass plate was evaluated as "? &Quot;, and the cohesive failure of the adhesive was evaluated as " x ". In addition, Comparative Example 8 hardened to a state where bonding was impossible, and Comparative Examples 10 and 11 could not be evaluated because they were uncured.

(Examples 14 to 15 and Comparative Examples 8 to 11)

As shown in Table 2, a photocurable composition and a curable composition were prepared in the same manner as in Example 13 except for changing the compounding materials. Then, in the same manner as in Example 13, the curability test and the adhesion test of the photocurable composition were carried out. The results are shown in Table 2.

The liquid-phase gaskets of Comparative Examples 9 to 11 had poor shape-retaining properties, and when the glass plate was bonded, the moisture spreads and could not be used as a gasket.

As shown in Table 2, the liquid-phase gasket according to the Example exhibited excellent shape retentivity without curing at the time of irradiation with active energy rays and had sufficient bonding time after irradiation with active energy rays. In addition, in the housing member joined using the liquid-phase gasket according to the embodiment, the housing member can be removed with a small force even at the initial stage of curing and after curing, The housing member can be recombined using the gasket as it is, and the seal performance such as the original waterproof performance is maintained even after the recombination.

Claims (12)

(A) an organic polymer containing a crosslinkable silicon group,
(B) a photobase generator,
(C1) at least one fluorine-based compound selected from the group consisting of a silicon compound having Si-F bonds and (C2) an alkali metal salt of boron fluoride, boron trifluoride complex, fluorinating agent and polyfunctional fluorine compound,
(D) a polyfunctional compound having at least one (meth) acryloyl group in one molecule
Wherein the photocurable composition is a photocurable composition. The photocurable composition according to claim 1, further comprising a crosslinkable silicon group-containing compound which generates at least one amino group selected from the group consisting of a primary amino group and a secondary amino group by (E) light. The photocurable composition according to any one of claims 1 to 3, further comprising (F) a monofunctional compound having a photopolymerizable unsaturated group. The photocurable composition according to any one of claims 1 to 3, further comprising (G) a tackifying resin. The organic electroluminescent device according to any one of claims 1 to 4, wherein the organic polymer (A) having a crosslinkable silicon group is selected from the group consisting of a polyoxyalkylene polymer containing a crosslinkable silicon group and a (meth) acrylic polymer containing a crosslinkable silicon group Wherein the photocurable composition is at least one selected from the group consisting of The photocurable composition according to any one of claims 1 to 5, wherein the photobase generator (B) is a photolatent tertiary amine. The organic electroluminescent device according to claim 5 or 6, wherein the (A) organic polymer having a crosslinkable silicon group is (a-1) a polymer having a crosslinkable silicon group and a photo radically polymerizable vinyl group in the molecule And (a-2) at least one polymer selected from the group consisting of organic polymers having a crosslinkable silicon group other than (a-1). A cured product formed by irradiating light to the photo-curable composition according to any one of claims 1 to 7. An article produced by using the photo-curing composition according to any one of claims 1 to 7. An article using the photocurable composition according to any one of claims 1 to 7 as an adhesive. An electronic device product made using the photo-curable composition according to any one of claims 1 to 7. As a rework method of an electronic device,
(A) a liquid phase gasket for a field forming mold for electronic equipment, comprising: (A) an organic polymer containing a crosslinkable silicon group; (B) a photobase generator; (C1) a silicon compound having Si- ) Preparing a field-shaping mold liquid gasket containing a polyfunctional compound having at least one (meth) acryloyl group in one molecule,
(B) applying the liquid gasket to an area where one housing member of the electronic apparatus is to be sealed in an uncured state, irradiating an active energy ray, and fitting the other housing member,
(C) a step of removing the housing member of the electronic device requiring the rework after curing and replacing the internal parts
And a rewinding method of the electronic device.