JP2017125098A - Method for curing photocurable adhesive, cured product, photocurable adhesive, and product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for curing a photocurable adhesive which has long heating stability at high temperature, and can control curing timing at desired timing; a cured product; a photocurable adhesive; and a product.SOLUTION: A method for curing a photocurable adhesive includes: a heating step of heating a photocurable adhesive containing a thermoplastic resin and a photo-latent curing catalyst at 50°C or higher; a coating step of coating the heated photocurable adhesive onto an adherend; and a curing step of irradiating the photocurable adhesive coated onto the adherent with light to cure the adherend.SELECTED DRAWING: None

Description

  The present invention relates to a method for curing a photocurable adhesive, a cured product, a photocurable adhesive, and a product. In particular, the present invention relates to a photocurable adhesive curing method, a cured product, a photocurable adhesive, and a product that are excellent in heat stability at high temperatures and can control the curing timing.

Conventionally, an organic polymer having a reactive silicon group represented by the following general formula (i), a resin solid at room temperature, a silane coupling agent having a reactive silicon group represented by the following general formula (ii), curing Moisture curable reactive hot melt adhesive compositions containing a catalyst are known.
-SiR ¹ _3-a X _a (i)
(In the formula, each R ¹ is independently at least one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. X Is a hydroxyl group or a hydrolyzable group, a is 1, 2 or 3.)
-SiR ¹ X ₂ (ii)
(Wherein R ¹ and X are the same as above)

  According to the moisture curable reactive hot melt adhesive composition described in Patent Document 1, it is possible to achieve both the thermal stability during heating and melting and the curability at room temperature after coating, and the moisture curable type with less toxicity. A reactive hot melt adhesive can be provided.

International Publication No. 2012/053478

  However, in the moisture-curable reactive hot melt adhesive composition described in Patent Document 1, as described in the Examples of Patent Document 1, the thermal stability at high temperature is about 1 hour 50 minutes at the longest. In addition to being short, the curing proceeds when exposed to moisture. For example, the curing of the adhesive composition proceeds from the time of application to the adherend with a dispenser or the like, and the curing timing cannot be controlled. In addition, since the moisture curable reactive hot melt adhesive composition described in Patent Document 1 is cured by touching moisture in the air, the equipment of a dispenser or the like used for application of the adhesive composition The discharge port is clogged by the curing of the adhesive composition.

  Accordingly, an object of the present invention is to provide a photocurable adhesive curing method, a cured product, a photocurable adhesive, and a product that have long heating stability at high temperatures and can control the curing timing to a desired timing. It is in.

  In order to achieve the above-mentioned object, the present invention provides a heating step of heating a photocurable adhesive containing a thermoplastic resin and a photolatent curing catalyst to 50 ° C. or more, and a heated photocurable adhesive. There is provided a method for curing a photocurable adhesive comprising an application step of applying to an adherend and a curing step of irradiating and curing the photocurable adhesive applied to the adherend.

  Moreover, in the said hardening method of a photocurable adhesive agent, it is preferable that a photocurable adhesive agent further contains the organic polymer which has a crosslinkable silicon group.

  Further, in the photocurable adhesive curing method, the photolatent curing catalyst is at least selected from the group consisting of a silicon compound having a Si—F bond used together with a photolatent compound, and a photobase generator. Preferably it contains one compound.

  Moreover, in the said hardening method of a photocurable adhesive agent, the photocurable adhesive produces | generates 1 or more types of amino groups selected from the group which consists of a primary amino group and a secondary amino group with light. It is preferable to further contain a functional silicon group-containing compound.

  In order to achieve the above object, the present invention provides a photocurable adhesive containing a thermoplastic resin and a photolatent curing catalyst, wherein the viscosity of the photocurable adhesive is 0.1 to 1,000 Pa · s. A heating process that heats the adhesive until it becomes, a coating process that applies the heated photocurable adhesive to the adherend, and a curing process that cures the photocurable adhesive applied to the adherend by irradiating light. A photocurable adhesive curing method comprising:

  Moreover, in the said hardening method of a photocurable adhesive agent, it is preferable that a photocurable adhesive agent further contains the organic polymer which has a crosslinkable silicon group.

  Moreover, in order to achieve the said objective, this invention provides the hardened | cured material of the photocurable adhesive obtained by the hardening method of the photocurable adhesive as described in any one of the said.

  Furthermore, in order to achieve the above object, the present invention provides a photocurable adhesive used for heat application containing a thermoplastic resin and a photolatent curing catalyst.

  Moreover, it is preferable that the said photocurable adhesive agent further contains the organic polymer which has a crosslinkable silicon group.

  In the photocurable adhesive, the photolatent curing catalyst is at least one compound selected from the group consisting of a silicon compound having a Si—F bond used together with a photolatent compound, and a photobase generator. It is preferable to contain.

  In the photocurable adhesive, the organic polymer having a crosslinkable silicon group is a polymer having a crosslinkable silicon group and a photoradically polymerizable vinyl group in the molecule (provided that it has a Si-F bond). One or more polymers selected from the group consisting of organic polymers having a crosslinkable silicon group other than a polymer having a crosslinkable silicon group and a photoradically polymerizable vinyl group in the molecule) It is preferable that

  The photocurable adhesive further contains a crosslinkable silicon group-containing compound that generates one or more amino groups selected from the group consisting of primary amino groups and secondary amino groups by light. Is preferred.

  In order to achieve the above object, the present invention provides a product formed using the photocurable adhesive described in any one of the above.

  According to the curing method, cured product, photocurable adhesive, and product of the photocurable adhesive of the present invention, the photocurable adhesive has long heat stability at high temperatures and can control the curing timing to a desired timing. Curing methods, cured products, photocurable adhesives, and products can be provided.

  By combining a predetermined thermoplastic resin and a predetermined photolatent curing catalyst, the present inventor does not substantially proceed with curing even when exposed to air containing moisture at a high temperature, and the irradiation of active energy is triggered. As a result, it was found that a photo-curable adhesive that cures rapidly can be obtained. The photocurable adhesive which concerns on this embodiment was created based on this knowledge. Hereinafter, it demonstrates in detail along embodiment.

  Specifically, the photocurable adhesive according to the present embodiment contains a thermoplastic resin and a photolatent curing catalyst. Moreover, it is preferable that the photocurable adhesive which concerns on this Embodiment further contains the organic polymer which has a liquid crosslinkable silicon group at normal temperature. In this embodiment, for convenience of explanation, an organic polymer having a crosslinkable silicon group (sometimes referred to as a crosslinkable silicon group-containing organic polymer) is an A component, a thermoplastic resin is a B component, and photolatent curing. A catalyst may be called C component. Moreover, in description of this Embodiment, the photocurable adhesive which concerns on this Embodiment may be called "the compound which concerns on this embodiment."

(Component A: Crosslinkable silicon group-containing organic polymer)
(A) The crosslinkable silicon group-containing organic polymer is not particularly limited as long as it is an organic polymer having a crosslinkable silicon group. In this embodiment, the main chain is an organic polymer that is not polysiloxane, and organic polymers having various main chain skeletons excluding polysiloxane are easily available, and cause of contact failure in the field of electrical applications. This is preferable in that it does not contain or generate low molecular cyclic siloxane. Further, as the (A) crosslinkable silicon group-containing organic polymer, (a-1) a polymer having a crosslinkable silicon group and a photoradically polymerizable vinyl group in the molecule can be used (however, Si Except those having a -F bond). Since the crosslinkable silicon group-containing organic polymer further has a photo-radically polymerizable vinyl group in the molecule, the initial tackiness and / or flexibility of the photocurable adhesive according to the present embodiment is further maintained. The heat resistance by post-curing can be further improved. Furthermore, as the crosslinkable silicon group-containing organic polymer (A), an organic polymer having a crosslinkable silicon group other than (a-2) (a-1) can also be used.

  (A) Specific examples of the main chain skeleton of the crosslinkable silicon group-containing organic polymer include polyoxyalkylene polymers such as polyoxypropylene, polyoxytetramethylene, and polyoxyethylene-polyoxypropylene copolymers. ; Hydrocarbon polymers such as ethylene-propylene copolymers, polyisobutylene, polyisoprene, polybutadiene, hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; 2 bases such as adipic acid Polyester polymer obtained by condensation of acid and glycol or ring-opening polymerization of lactones; (meth) acrylic acid ester obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate Polymer: (meth) acrylic acid ester monomer, vinyl acetate, acrylo Vinyl polymer obtained by radical polymerization of monomers such as tolyl and styrene; Graft polymer obtained by polymerizing vinyl monomer in organic polymer; Polysulfide polymer; Polyamide polymer; Polycarbonate polymer A diallyl phthalate polymer and the like. These skeletons may be contained alone in (A) the crosslinkable silicon group-containing organic polymer, or two or more kinds may be contained in blocks or randomly.

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

  (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 general formula (1) is suitable.

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

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

  The hydrolyzable group represented by X is not particularly limited as long as it is other than F atom. Examples thereof include an alkoxy group, an acyloxy group, an amino group, an amide group, an aminooxy group, and an alkenyloxy group. In these, an alkoxy group is preferable from a viewpoint that hydrolysis property is moderate and it is easy to handle. Among the alkoxy groups, those having a smaller number of carbon atoms have higher reactivity, and the reactivity increases as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group. Although it can be selected according to the purpose and application, a methoxy group or an ethoxy group is usually used.

Specific examples of the crosslinkable silicon group include trialkoxysilyl groups [—Si (OR) ₃ ] such as trimethoxysilyl group and triethoxysilyl group, dialkoxy such as methyldimethoxysilyl group and methyldiethoxysilyl group. A silyl group [—SiR ¹ (OR) ₂ ] can be mentioned, a trialkoxysilyl group [—Si (OR) ₃ ] is preferable in terms of high reactivity, and a trimethoxysilyl group is more preferable. Here, R is an alkyl group such as a methyl group or an ethyl group. The photocurable adhesive according to the present embodiment uses a polymer having a highly reactive trimethoxysilyl group, and has excellent stability without curing even when heated to a high temperature of about 100 ° C. Show. Thus, although it is thermally stable, it cures quickly by light irradiation. Therefore, the trimethoxysilyl group is most preferable as the crosslinkable silicon group for the production of the photocurable adhesive.

  Moreover, a crosslinkable silicon group may be used by 1 type and may be used together 2 or more types. The crosslinkable silicon group can be present in the main chain, the side chain, or both. Moreover, the crosslinkable silicon group shown by several general formula (1) may mutually be connected. In this case, the number of silicon atoms forming the crosslinkable silicon group is one or more, but in the case of silicon atoms linked by a siloxane bond or the like, the number of silicon atoms is preferably 20 or less. Examples of the photo-radically polymerizable vinyl group include a group containing a (meth) acryloyl group such as a (meth) acryloyloxy group.

  Each of the organic polymer having a crosslinkable silicon group and the organic polymer having a crosslinkable silicon group and a photoradically polymerizable vinyl group may have a straight chain or a branch, and the number average molecular weight is It is about 500 to 100,000 in terms of polystyrene in GPC, more preferably 1,000 to 50,000, and particularly preferably 3,000 to 30,000. If the number average molecular weight is less than 500, the cured product tends to be inconvenient in terms of elongation characteristics, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity. In addition, it is desirable that the number average molecular weight is high from the viewpoint of ensuring the flexibility of the cured product obtained by post-curing the pressure-sensitive adhesive.

  In order to obtain a rubber-like cured product having high strength, high elongation, and low elastic modulus, a crosslinkable silicon group, a crosslinkable silicon group and a photo-radical polymerizable polymer contained in the organic polymer having a crosslinkable silicon group are used. The crosslinkable silicon group and photoradically polymerizable vinyl group contained in the organic polymer having a vinyl group average 0.8 or more, preferably 1.0 or more, more in one polymer molecule. Preferably 1.1 to 5 are present. If the number of crosslinkable silicon groups and radically polymerizable vinyl groups contained in the molecule is less than 0.8 on average, the curability will be insufficient and good rubber elastic behavior will not be exhibited. Become. From the viewpoint of reducing the crosslink density, it is preferable to use an organic polymer having an average number of crosslinkable silicon groups in the molecule of 1.0 or less in combination. The crosslinkable silicon group and the photoradically polymerizable vinyl group may be at the end of the main chain of the organic polymer molecular chain, at the end of the side chain, or at both. In particular, when the crosslinkable silicon group is only at the end of the main chain of the molecular chain, the effective network length of the organic polymer component contained in the finally formed cured product is increased, so that the high strength, high elongation, A rubber-like cured product having a low elastic modulus is easily obtained.

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

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

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

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

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

  As a specific example of the polymer reaction method, hydrosilylation or mercaptoization is carried out by reacting an unsaturated group-containing polyoxyalkylene polymer with a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group. Examples thereof include a method for obtaining a polyoxyalkylene polymer having a group. An unsaturated group-containing polyoxyalkylene-based polymer is obtained by reacting an organic polymer having a functional group such as a hydroxyl group with an organic compound having an active group and an unsaturated group that are reactive with the functional group. A polyoxyalkylene polymer containing can be obtained.

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

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

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

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

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

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

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

  Various monomers can be used as the (meth) acrylic acid ester monomer constituting the main chain of the (meth) acrylic acid ester polymer. For example, (meth) acrylic acid monomers such as acrylic acid; (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid n-butyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic (Meth) acrylic acid alkyl ester monomers such as stearyl acid; alicyclic (meth) acrylic acid ester monomers; aromatic (meth) acrylic acid ester monomers; (meth) acrylic acid 2-methoxyethyl (meta) ) Acrylic ester monomers; silyl group-containing (meth) acrylic ester monomers such as γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane; (meth) acrylic acid derivatives; Fluorine-containing (meth) acrylic acid ester monomers It is.

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

  These may be used alone or may be copolymerized. From the physical properties of the product, a polymer composed of a (meth) acrylic acid monomer is preferred. Moreover, the (meth) acrylic acid ester type polymer which used the 1 type (s) or 2 or more types (meth) acrylic-acid alkylester monomer and used together with the other (meth) acrylic acid monomer as needed is more preferable. Furthermore, the number of silicon groups in the (meth) acrylic acid ester polymer (A) can be controlled by using a silyl group-containing (meth) acrylic acid ester monomer in combination. A methacrylic acid ester polymer comprising a methacrylic acid ester monomer is particularly preferred because of its good adhesion. In addition, when the viscosity is reduced, the flexibility is imparted, and the tackiness is imparted, it is preferable to use an acrylate monomer as appropriate. In the present embodiment, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

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

  Examples of the controlled radical polymerization method include a free radical polymerization method and a living radical polymerization method using a chain transfer agent having a specific functional group, and an addition-fragmentation chain transfer (RAFT) polymerization method, Living radical polymerization methods such as a radical polymerization method using a transition metal complex (Transition-Metal-Mediated Living Radical Polymerization) are more preferable. Further, a reaction using a thiol compound having a reactive silyl group and a reaction using a thiol compound having a reactive silyl group and a metallocene compound are also suitable.

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

  These organic polymers having a crosslinkable silicon group and / or a 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 photoradically polymerizable vinyl group, and a saturated hydrocarbon polymer having a crosslinkable silicon group and / or a photoradically polymerizable vinyl group In addition, an organic polymer obtained by blending two or more selected from the group consisting of a (meth) acrylic acid ester-based polymer having a crosslinkable silicon group and / or a radically polymerizable vinyl group can also be used. In particular, an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group has excellent characteristics. When applied to the photocurable adhesive according to the present embodiment, the tensile shear adhesive force and the adhesive force can be increased.

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

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

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

  The molecular chain of the (meth) acrylic ester copolymer is substantially composed of monomer units of the formulas (3) and (4). Here, “substantially” means that the total of the monomer units of the formula (3) and the formula (4) present in the copolymer exceeds 50% by mass. The total of the monomer units of the formula (3) and the formula (4) is preferably 70% by 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, and more preferably 90:10 to 60:40, by mass ratio.

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

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

  Furthermore, in this embodiment, an organic polymer obtained by blending a saturated hydrocarbon polymer having a crosslinkable silicon group and a (meth) acrylic acid ester copolymer having a crosslinkable silicon group can also be used. As another method for producing an organic polymer obtained by blending a (meth) acrylic acid ester-based copolymer having a crosslinkable silicon group, in the presence of an organic polymer having a crosslinkable silicon group (meta ) A method of polymerizing an acrylate monomer can be used.

(B component: thermoplastic resin)
The photocurable adhesive which concerns on this embodiment contains the thermoplastic resin which is solid at normal temperature (23 degreeC). Examples of thermoplastic resins include acrylic polymers, methacrylic polymers, polyvinyl acetate, polystyrene derivatives, polyisobutene, polyolefins, polyalkylene oxides, polyurethanes, polyamides, natural rubber, polybutadiene, polyesters, and polycarbonates. , Wax, epoxy resin, polyisoprene, nitrobutadiene rubber (NBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene Block copolymer (SEBS), hydrogenated nitrobutadiene rubber (hydrogenated NBR), hydrogenated styrene-butadiene-styrene block copolymer (hydrogenated SBS), hydrogenated styrene-isoprene-styrene block copolymer (Hydrogenated SIS), and hydrogenated styrene - ethylene - butylene - styrene block copolymer (hydrogenated SEBS) and the like. In order to improve heat resistance, it is preferable to select a resin having a hydrolyzable group in the molecule as the thermoplastic resin. These may be used alone or in combination of two or more.

  Preferably, (B-1) (meth) acrylic acid ester (co) polymer can be used as the thermoplastic resin. In addition, when the thermoplastic resin according to the present embodiment includes the component A, the thermoplastic resin may be various resins as long as the mixture is mixed with the component A having fluidity at room temperature to solidify the mixture. Can be used. In this embodiment, the (B-1) (meth) acrylic acid ester-based (co) polymer and / or (B-2) tackifier resin has other compatibility such as compatibility with the A component and adhesiveness. This is particularly preferable from the viewpoint of securing a balance of physical properties.

[(B-1) (Meth) acrylic ester (co) polymer]
(Meth) acrylic acid ester-based (co) polymer (B-1) (hereinafter sometimes referred to as (co) polymer (B-1)) is one type of (meth) acrylic as a repeating unit. A polymer composed of an acid ester compound, a copolymer composed of a plurality of (meth) acrylic acid ester compounds as repeating units, and one or more (meth) acrylic acid ester compounds as repeating units, and A copolymer comprising a copolymerizable compound. In addition, description with "(meth) acrylic acid ester" shows acrylic acid ester and / or methacrylic acid ester.

  Various monomers can be used as the (meth) acrylic acid ester monomer constituting the main chain of the polymer composed of the (meth) acrylic acid ester compound. For example, (meth) acrylic acid monomers such as acrylic acid; (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid n-butyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic (Meth) acrylic acid alkyl ester monomers such as stearyl acid; alicyclic (meth) acrylic acid ester monomers; aromatic (meth) acrylic acid ester monomers; (meth) acrylic acid 2-methoxyethyl (meta) ) Acrylic ester monomers; silyl group-containing (meth) acrylic ester monomers such as γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane; (meth) acrylic acid derivatives; Fluorine-containing (meth) acrylic acid ester monomers It is. In the present embodiment, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. These may be used alone or may be copolymerized. Moreover, the (meth) acrylic acid ester-type polymer which used the 1 type (s) or 2 or more types (meth) acrylic-acid alkylester monomer, and used together with the other (meth) acrylic acid monomer as needed can also be used.

  The main chain skeleton of the (meth) acrylate (co) polymer (B-1) is substantially composed of one or more (meth) acrylate compounds. Here, “substantially” means that the proportion of the repeating unit derived from the (meth) acrylic acid ester compound present in the (co) polymer (B-1) exceeds 50%. Moreover, 70% or more of the ratio of the repeating unit derived from the (meth) acrylic acid ester compound which exists in (co) polymer (B-1) is preferable.

  Furthermore, among the (meth) acrylic acid ester compounds, from the viewpoint of compatibility and stability, the molecular chain is substantially (b-1) a (meth) acrylic acid ester compound having an alkyl group having 1 to 8 carbon atoms. And a copolymer (hereinafter referred to as (co) polymer (B-1) -a) (b-2) a (meth) acrylic acid ester compound having an alkyl group having 10 or more carbon atoms. ) Is preferred.

The (co) polymer (B-1) -a (b-1) (meth) acrylic acid ester compound having an alkyl group having 1 to 8 carbon atoms is represented by the general formula (5):
CH ₂ = C (R ⁶ ) COOR ⁷ (5)
(Wherein R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents an alkyl group having 1 to 8 carbon atoms). Examples of R ⁷ described in the general formula (5) include alkyl groups having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms. Note that R ⁷ in the (co) polymer (B-1) -a may be one type of alkyl group or two or more types of alkyl groups.

In addition, the (b-2) (meth) acrylic acid ester compound having an alkyl group having 10 or more carbon atoms in the (co) polymer (B-1) -a has the general formula (6):
CH ₂ = C (R ⁶ ) COOR ⁸ (6)
(Wherein R ⁶ is the same as in the general formula (5). R ⁸ represents an alkyl group having 10 or more carbon atoms).

As R ⁸ described in the general formula (6), for example, a lauryl group, a tridecyl group, a cetyl group, a stearyl group, an alkyl group having 22 carbon atoms, a carbon number of 10 or more, such as a biphenyl group, preferably 10-30, More preferably, a 10-20 long-chain alkyl group is mentioned. In addition, R ⁸ in the (co) polymer (B-1) -a may be one type of alkyl group or two or more types of alkyl groups.

  The molecular chain of the (co) polymer (B-1) -a consists essentially of the compounds (b-1) and (b-2). Here, substantially consisting of the compounds (b-1) and (b-2) means that (b-1) and (b-2) existing in the (co) polymer (B-1) -a. It means that the ratio of the repeating unit derived from the compound exceeds 50%.

  The proportion of repeating units derived from the compounds (b-1) and (b-2) present in the (co) polymer (B-1) -a is preferably 70% or more. An organic polymer having a crosslinkable silicon group when the proportion of repeating units derived from the compounds (b-1) and (b-2) present in the (co) polymer (B-1) -a is less than 50%. There is a tendency that the compatibility between (A) and the (co) polymer (B-1) -a is lowered, and there is a tendency to become cloudy and the adhesive properties of the cured product are lowered.

  Moreover, the ratio of the repeating unit derived from the compounds (b-1) and (b-2) present in the (co) polymer (B-1) -a is a weight ratio (derived from (b-1) :( b-2)) is preferably 95: 5 to 40:60, more preferably 90:10 to 60:40. When the ratio is larger than 95: 5, the compatibility is lowered, and when it is smaller than 40:60, the cost tends to be disadvantageous.

  Further, in the (co) polymer (B-1), in addition to the repeating unit derived from the (meth) acrylic acid ester compound, a repeating unit derived from a compound copolymerizable with these can also be included. Examples of the compound having copolymerizability with the (meth) acrylic acid ester compound include compounds containing acrylic acid, amide group, epoxy group, amino group, other acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, Examples thereof include compounds derived from vinyl acetate, vinyl propionate, ethylene and the like.

  As for the molecular weight of the (co) polymer (B-1) component, for example, the number average molecular weight in terms of polystyrene in GPC is preferably 500 to 100,000, more preferably 1,000 to 50,000. 2,000 to 20,000 is particularly preferable because of easy handling and excellent adhesive properties.

  Examples of the method for producing the (co) polymer (B-1) include a solution polymerization method using a radical reaction and a bulk polymerization method. In addition, it is preferable that the (co) polymer (B-1) has a crosslinkable silicon group represented by the general formula (1) because the cured product obtained has excellent adhesive strength and heat resistance. . As the crosslinkable silicon group represented by the general formula (1), for example, from the viewpoint of obtaining high activity and good curability, a dimethoxymethylsilyl group, a trimethoxysilyl group, and a triethoxysilyl group are preferable. A dimethoxymethylsilyl group is more preferable from the viewpoint of hardly forming a gelled product when melted.

As a method for introducing a reactive silicon group into the (co) polymer (B-1), various methods may be mentioned. For example, (i) a compound having a polymerizable unsaturated bond and a reactive silicon group is compounded. A method of copolymerizing with (b-1) and (b-2), (ii) a compound (for example, acrylic acid) having a polymerizable unsaturated bond and a reactive functional group (hereinafter referred to as Y ′ group) as a compound ( After copolymerization with b-1) and (b-2), a compound having a functional group capable of reacting with the crosslinkable silicon group and Y ′ group (hereinafter referred to as Y ″ group) (for example, , A method of reacting an isocyanate group and a compound having —Si (OCH ₃ ) group), (iii) compounds (b-1) and (b-2) in the presence of a mercaptan having a crosslinkable silicon group as a chain transfer agent (Iv) crosslinkable silicon A method in which the compounds (b-1) and (b-2) are copolymerized using an azobisnitrile compound or a disulfide compound having an initiator, and (v) a compound (b-1) or (b-2) by a living radical polymerization method. And the like, and a crosslinkable silicon group is introduced at the molecular terminal.

  The number of crosslinkable silicon groups in the (co) polymer (B-1) is not particularly limited, and from the viewpoint of the effect on adhesive strength and cost, the (co) polymer (B-1) in one molecule. The average is preferably 0.1 or more and 4.0 or less, and more preferably 0.5 or more and 2.0 or less.

[(B-2) Tackifying resin]
The tackifying resin is not particularly limited and includes resins that are usually used. Specific examples include terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, hydrogenated aromatic modified terpene resins, terpene-phenol resins obtained by copolymerizing terpenes with phenols, phenol resins, hydrogenated terpene phenol resins. , Modified phenolic resin, xylene resin, xylene-phenolic resin, cyclopentadiene resin, cyclopentadiene-phenolic resin; α-methylstyrene single-polymerized resin, styrene-based single-polymerized resin, etc., low molecular weight styrene-based resin; α-methylstyrene / Styrene copolymer resin, styrene monomer / aliphatic monomer copolymer resin, styrene monomer / α-methylstyrene / aliphatic monomer copolymer resin, styrene monomer / aromatic monomer copolymer resin Styrene copolymer resins such as petroleum resin ( In example, C5 hydrocarbon resins, C9 hydrocarbon resins, C5, C9 hydrocarbon copolymer resins, C5, C9 hydrocarbons, such as phenol copolymer resin), hydrogenated petroleum resins. These may be used alone or in combination of two or more.

  Here, as the tackifier resin, it is preferable to select a resin having a polarity that matches the polarity of the adherend. For example, when the photocurable adhesive according to the present embodiment is used for an adherend having a low polarity, it is preferable to use a tackifying resin having a low polarity, and the adherend having a high polarity is related to the present embodiment. When using a photocurable adhesive, it is preferable to use a highly polar tackifying resin. When using the photocurable adhesive according to the present embodiment for a wide range of adherends from high polarity adherends to low polarity adherends, a low polarity tackifier resin and a high polarity tackifier resin; It is preferable to mix and use.

  And as a tackifier resin, a terpene phenol resin and a styrene copolymer resin are preferable from a viewpoint with good compatibility with the organic polymer which has a crosslinkable silicon group. Moreover, from the viewpoint of improving the adhesion between the organic polymer having a crosslinkable silicon group and poor adherence but having a low polarity, a small amount of hydrogenated aromatic modified terpene resin may be added. As a tackifying resin, from the viewpoint of heat stability, heat stability during preparation of a photocurable adhesive (ie, stability that does not substantially gel) and heat stability during use are ensured or improved. More preferred are terpene phenol resins, low molecular weight styrene resins, and styrene copolymer resins. Also, terpene phenol resin, low molecular weight styrene resin, styrene monomer / aliphatic monomer copolymer resin, styrene monomer / α-methylstyrene / aliphatic monomer copolymer resin, styrene monomer / indene / fatty An aromatic monomer copolymer resin is more preferable, and a terpene phenol resin and a styrene monomer / aliphatic monomer copolymer resin are particularly preferable. And as a tackifier resin, the terpene phenol resin is the most preferable from a viewpoint which is excellent in adhesive strength with heat stability.

  10-200 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for the usage-amount of tackifying resin (B-2), 10-150 mass parts is more preferable. When the amount is less than 10 parts by mass, the adhesive strength is insufficient. When the amount is more than 150 parts by mass, the cured product becomes too hard and the adhesive strength is insufficient, and the viscosity increases and the workability decreases.

(C component: photolatent curable resin)
As the photolatent curing catalyst, a compound that does not substantially cure the curing of the photocurable adhesive even at a high temperature of about 80 ° C. to 100 ° C. can be used, and is a compound that generates an acid or a base by irradiation with light. It is particularly preferred. A compound that generates a base upon irradiation with light is preferred because it does not inhibit moisture or cause rust on the adherend. Specifically, the (C) photolatent curing catalyst is at least selected from the group consisting of (C1) a silicon compound having a Si—F bond used together with a photolatent compound, and (D) a photobase generator. One compound is mentioned. (C1) As the silicon compound having a Si—F bond, various compounds including a silicon group having a Si—F bond (hereinafter sometimes referred to as a fluorosilyl group) can be used. As the silicon compound as the component (C1), any of inorganic compounds and organic compounds can be used. In the present embodiment, an organic compound having a fluorosilyl group is preferable, and an organic polymer having a fluorosilyl group is more preferable because of high safety. Moreover, the low molecular organosilicon compound which has a fluoro silyl group from the point from which a compound becomes low viscosity is preferable.

  (C1) A silicon compound having a Si—F bond is used together with a photolatent compound to act as a curing catalyst for (A) a crosslinkable silicon group-containing organic polymer. (C1) As the silicon compound having a Si-F bond, various compounds including a silicon group having a Si-F bond (hereinafter sometimes referred to as a fluorosilyl group) can be used, and there is no particular limitation. Either a low molecular compound or a high molecular compound can be used. An organosilicon compound having a fluorosilyl group is preferable, and an organic polymer having a fluorosilyl group is more preferable because of high safety. Moreover, the low molecular organosilicon compound which has a fluoro silyl group from the point from which a compound becomes low viscosity is preferable.

  (C1) Specific examples of the silicon compound having a Si—F bond include fluorosilanes described in WO2015-088021 represented by formula (7), and WO2015-088021 represented by formula (8). Preferred examples include compounds having a fluorosilyl group described below (hereinafter also referred to as fluorinated compounds) and organic polymers having a fluorosilyl group described in WO2015-088021 (hereinafter also referred to as fluorinated polymers). As mentioned.

R ⁹ _4-d SiF _d (7)
(In Formula (7), each R ⁹ is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ¹⁰ SiO— (R ¹⁰ is independently each having 1 to 20 carbon atoms. Or a substituted or unsubstituted hydrocarbon group, or a fluorine atom), d is any one of 1 to 3, and d is preferably 3. R ⁹ And when there are a plurality of R ^{10 s} , they may be the same or different.)

-SiF _d R ⁹ _e Z _f (8)
(In Formula (8), R < ⁹ > and d are respectively the same as Formula (7), Z is respectively independently the other hydrolysable group except a hydroxyl group or a fluorine, and e is either 0-2. F is any one of 0 to 2, and d + e + f is 3. When a plurality of R ⁹ , R ¹⁰ and Z are present, they may be the same or different.

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

In the compound having a fluorosilyl group represented by the formula (8), the hydrolyzable group represented by Z is preferably an alkoxy group from the viewpoint of mild hydrolyzability and easy handling, and R ⁹ is a methyl group. preferable.

When the fluorosilyl group represented by the formula (8) is exemplified, a silicon group having no hydrolyzable group other than fluorine or a fluorosilyl group in which R ⁹ is a methyl group are preferable, and a trifluorosilyl group is more preferable.

  The compound having a fluorosilyl group represented by the formula (8) is not particularly limited, and either a monomolecular compound or a polymer compound can be used. For example, inorganic silicon compounds; low molecular organic silicon compounds such as vinyl difluoromethoxysilane, vinyl trifluorosilane, phenyldifluoromethoxysilane, and phenyltrifluorosilane; fluorinated poly having a fluorosilyl group represented by formula (8) Examples thereof include polymer compounds such as siloxane, and preferred are fluorosilanes represented by the formula (7) and polymers having a fluorosilyl group represented by the formula (8) at the end of the main chain or side chain.

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

  The fluorinated polymer is a single polymer in which the main chain skeleton is the same as a fluorosilyl group, that is, the number of fluorosilyl groups per molecule, the bonding position thereof, and the number of Fs that the fluorosilyl group has, and The polymer may be a single polymer having the same main chain skeleton, or may be a mixture of a plurality of polymers, any or all of which are different. Any of these fluorinated polymers can be suitably used as a resin component of a photo-curing adhesive exhibiting rapid 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, the cured product tends to be disadvantageous in terms of elongation characteristics, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity.

  (C1) Although there is no restriction | limiting in particular in the mixture ratio of the silicon compound which has a Si-F bond, When using a high molecular compound with a number average molecular weight 3,000 or more, such as a fluorinated polymer, as a component (C1), (A) The amount is preferably 0.01 to 80 parts by weight, more preferably 0.01 to 30 parts by weight, and still more preferably 0.05 to 20 parts by weight with respect to 100 parts by weight of the crosslinkable silicon group-containing organic 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 low molecular organic compound having a fluorosilane group represented by the formula (7) or a fluorosilyl group represented by the formula (8) In the case of using a silicon compound, an inorganic silicon compound having a fluorosilyl group, etc., (A) 0.01 to 10 parts by mass is preferable with respect to 100 parts by mass of the crosslinkable silicon group-containing organic polymer. 5 parts by mass is more preferable.

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

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

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

  Examples of acyclic amidines include guanidine compounds and biguanide compounds described in WO2015-088021. Among the non-cyclic amidine compounds, for example, a photobase generator for generating an aryl-substituted guanidine compound or an aryl-substituted biguanide compound described in WO2015-088021 is used as a catalyst for the polymer (A). It is preferable because it shows a tendency to improve the curability of the surface, and a tendency to improve the adhesion of the resulting cured product.

  Examples of cyclic amidines include cyclic guanidine compounds, imidazoline compounds, imidazole compounds, tetrahydropyrimidine compounds, triazabicycloalkene compounds, and diazabicycloalkene compounds described in WO2015-088021. It is done.

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

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

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

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

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

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

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

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

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

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

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

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

  Among the photobase generators (D), photolatent tertiary amines are preferable from the viewpoint that the generated bases exhibit high catalytic activity, and the base generation efficiency is high and the storage stability as a composition is good. , Benzylammonium salt derivatives, benzyl-substituted amine derivatives, α-aminoketone derivatives and α-ammonium ketone derivatives are preferred. In particular, an α-aminoketone derivative and an α-ammonium ketone derivative are more preferable because the base generation efficiency is better, and an α-aminoketone derivative is more preferable than the solubility in the blend. Among α-aminoketone derivatives, α-aminoketone compounds that generate amidines from the basic strength of the generated base are preferable, and tertiary amines having a tertiary amine group composed of one nitrogen atom are more readily available. And α-aminoketone compounds that generate the same.

  These photobase generators (D) may be used alone or in combination of two or more. The mixing ratio of the photobase generator (D) is not particularly limited, but is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the (A) crosslinkable silicon group-containing organic polymer, and 0.1 to 40 A mass part is more preferable and 0.2-15 mass parts is still more preferable.

(Other compounding substances)
The photocurable adhesive of this embodiment includes, as necessary, (E) a crosslinkable silicon group-containing compound that generates an amino group by light, a silane coupling agent (adhesion imparting agent), and a photoradical initiator. , Photosensitizers, extenders, diluents, plasticizers, moisture absorbers, other condensation reaction promoting catalysts excluding component (C) and (D), compounds having epoxy groups, radical polymerizable functional groups Compounds, property modifiers that improve tensile properties, reinforcing agents, colorants, flame retardants, anti-sagging agents, antioxidants, anti-aging agents, UV absorbers, solvents, fragrances, pigments, dyes, waxes, resin fillers Various additives such as conductive powder, heat conductive powder, and phosphor may be added.

  The formulation according to this embodiment further comprises (E) a crosslinkable silicon group-containing compound that generates one or more amino groups selected from the group consisting of primary amino groups and secondary amino groups by light. It can also be included. (E) The crosslinkable silicon group-containing compound that generates one or more amino groups selected from the group consisting of a primary amino group and a secondary amino group by light adheres to the formulation according to this embodiment. Property can be imparted or adhesion can be improved. Thereby, the compound which concerns on this embodiment can be used suitably as an adhesive agent use.

  (E) The crosslinkable silicon group-containing compound that generates one or more amino groups selected from the group consisting of a primary amino group and a secondary amino group by light may be a primary amino group by light irradiation. Any compound that generates an aminosilane compound having at least one amino group selected from the group consisting of a group and a secondary amino group and a crosslinkable silicon group can be used. In this embodiment, the crosslinkable silicon group-containing compound that generates one or more amino groups 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 improving adhesiveness. The crosslinkable silicon group is preferably a silicon-containing group to which a hydrolyzable group is bonded. Among these, alkoxy groups such as a methoxy group and an ethoxy group are preferable because they are mildly hydrolyzable and easy to handle. In the aminosilane compound, the hydrolyzable group and the hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, preferably 2 or more, particularly preferably 3.

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

  Examples of the photoaminosilane generating compound include a silicon compound having an optical functional group described in WO2015-088021 represented by formulas (9) to (10), an aromatic sulfonamide derivative, an O-acyloxime derivative, and trans- Examples thereof include O-coumaric acid derivatives.

In formula (9), n is an integer of 1 to 3, Y represents a hydroxyl group or a hydrolyzable group, and an alkoxy group is preferable. When a plurality of Y are present, they may be the same or different. R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a substituent, vinyl group, allyl group, unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, unsubstituted or substituted aryl group. Is preferred. When a plurality of R ¹¹ are present, they may be the same or different. R ¹² is a hydrogen atom or an organic group, preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having a substituent, and more preferably a hydrogen atom. h is an integer of 1 to 5, and j is an integer of 1 to 6. R ¹³ is a substituted or unsubstituted hydrocarbon group bonded to a silicon atom and a nitrogen atom at h + j different carbon atoms, and a plurality of substituted or unsubstituted groups bonded to each other via one or more ether oxygen atoms. It is an h + j-valent group selected from the group consisting of hydrocarbon groups and has a molecular weight of 1,000 or less. R ¹² and R ¹³ may combine with each other to form a cyclic structure, and may include a hetero atom bond. Z is an oxygen atom or a sulfur atom, preferably an oxygen atom. Q represents a photofunctional group.

In formula (10), n, Y, R ¹¹ , Z, and Q are the same as in formula (9). R ¹⁵ 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 via one or more ether oxygen atoms. . t is an integer of 1 or more, and 1 or 2 is preferable. When t is 2 or more, t groups bonded to R ¹⁴ may be the same or different. R ¹⁴ 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 ¹⁴ and R ¹⁵ may be bonded to each other to form a cyclic structure, and may include a hetero atom bond.

  The photofunctional group Q is a known photosensitive group and is not particularly limited. Examples thereof include a group having a cyclic structure described in WO2015-088021, an oxime residue, and these substituted groups. A group having a 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, and a substituted group, and an aromatic group is preferable. Further, groups in the photofunctional group may be bonded to each other to form a cyclic structure.

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

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

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

  Examples of the —OQ group in which the photofunctional group Q is a p-nitrobenzyl group include (2,4-dinitrobenzyl) oxy group, (4-nitrobenzyl) oxy group, and [1- (4-nitronaphthalene) methyl. Nitrobenzyloxy group such as oxy group.

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

  In the formulas (9) and (10), examples of the residue excluding the ZQ group include 3- (trimethoxysilyl) propylaminocarbonyl group, 3- (triethoxysilyl) propylaminocarbonyl group, 3- (methyl Monoaminocarbonyl groups such as dimethoxysilyl) propylaminocarbonyl group and 3- (methyldiethoxysilyl) propylaminocarbonyl group; N- [3- (trimethoxysilyl) propyl] ethylenediaminocarbonyl group, N, N′-bis Examples include diaminocarbonyl groups such as [3- (trimethoxysilyl) propyl] ethylenediaminocarbonyl group; and aminocarbonyl groups such as triaminocarbonyl group such as N- [3- (trimethoxysilyl) propyl] diethylenetriaminocarbonyl group. .

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

  Although there is no restriction | limiting in particular in the mixture ratio of a photoaminosilane generating compound, 0.01-50 mass parts is preferable with respect to 100 mass parts of (A) crosslinkable silicon group containing organic polymer, and 0.1-30 mass parts is 0.1-30 mass parts. More preferably, 0.1-20 mass parts is still more preferable. These photoaminosilane generating compounds may be used alone or in combination of two or more.

  By mix | blending a silane coupling agent with the compound which concerns on this embodiment, the adhesiveness of the compound which concerns on this embodiment with respect to general adherends, such as a metal, a plastics, glass, can be improved.

  Examples of silane coupling agents 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; Alkyl silanes; phenyl group-containing silanes; isocyanurate group-containing silanes, and the like, but are not limited thereto. Also, modified amino group-containing silanes in which amino groups are modified by reacting amino group-containing silanes with epoxy group-containing compounds, isocyanate group-containing compounds, and (meth) acryloyl group-containing compounds containing the above silanes are used. May be.

  In addition, when the adherend is made of metal and a terpene-based tackifying resin is used, an organic polymer having a tackifying resin and a crosslinkable silicon group is used from the viewpoint of suppressing a decrease in the adhesive strength over time. A silane coupling agent may be added for the purpose of crosslinking. When a tackifying resin containing phenol or carboxylic acid is used, for example, by adding epoxysilane, the organic polymer having a crosslinkable silicon group and the tackifying resin can be cross-linked, thereby improving the adhesive strength. , Improvement of heat-resistant creep, and change in adhesive force due to movement of the tackifier resin over time can be suppressed.

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

  Examples of the photoradical 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 increasing the molecular weight thereof. Is mentioned.

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

  There is no particular limitation on the flash point of the diluent, but considering the safety of the resulting composition according to this embodiment, it is desirable that the flash point of the composition according to this embodiment is higher, the composition according to this embodiment It is preferable that there are few volatile substances from a thing. Therefore, the flash point of the diluent is preferably 60 ° C. or higher, and more preferably 70 ° C. or higher. When mixing 2 or more types of diluents, it is preferable that the flash point of the mixed diluent is 70 degreeC or more. In general, since a diluent having a high flash point tends to have a low dilution effect on the formulation according to the present embodiment, the flash point is preferably 250 ° C. or lower.

  Considering both the safety and the dilution effect of the formulation according to this embodiment, a saturated hydrocarbon solvent is preferable as the diluent, and normal paraffin and isoparaffin are more preferable. The normal paraffin and isoparaffin preferably have 10 to 16 carbon atoms.

  The mixing ratio of the diluent is not particularly limited, but 0 to 25% of the diluent is blended with respect to the unit weight of the blend according to the present embodiment from the viewpoint of the balance between the improvement of coating workability and the decrease in physical properties due to blending. It is preferable that 0.1 to 15% is added, and 1 to 7% is more preferable. A diluent may be used independently or may use 2 or more types together.

  As the other condensation reaction promoting catalyst excluding component (C) and (D), various condensation reaction promoting catalysts can be used, and there is no particular limitation. For example, organic metal compounds, bases such as acids and amines can be mentioned. Examples of organometallic compounds include: organotin compounds; dialkyltin oxides; reactants of dibutyltin oxide and phthalates; titanates; organoaluminum compounds; chelate compounds such as titanium tetraacetylacetonate; Examples include organic acid bismuth, boron trifluoride, boron trifluoride complexes, fluorinating agents, and alkali metal salts of polyvalent fluoro compounds. Examples of the silanol condensation catalyst include various other acidic catalysts and basic catalysts. However, the toxicity of the compound according to the present embodiment obtained may be increased depending on the amount of the organotin compound added. In this embodiment, since the component (C) and the component (D) act as a condensation reaction promoting catalyst, when using a curing catalyst other than these, it is used within a range in which the object and effect of this embodiment can be achieved. preferable.

  Examples of the compound having an epoxy group include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, aliphatic cyclic epoxy resin, brominated epoxy resin, and rubber. Examples include modified epoxy resins, urethane modified epoxy resins, glycidyl ester compounds, epoxidized polybutadiene, and epoxidized SBS (SBS represents a styrene-butadiene-styrene copolymer). When a compound having an epoxy group is further used as an additive, the formulation according to this embodiment exhibits high adhesion and durability after curing, and is particularly effective for adherends having an aromatic ring. In addition, when used in combination with an aminosilane compound, the adhesiveness is further improved.

  As the compound having a radical polymerizable functional group, an organic compound having at least one group selected from the group consisting of a radical polymerizable vinyl group, vinylidene group, and vinylene group can be used. In particular, it is preferable to use an organic compound having a vinyl group. As an example, from the viewpoint of improving reactivity, the radical polymerizable functional group is preferably at least one group selected from the group consisting of an acryloyl group and a methacryloyl group. As the organic compound, for example, a compound having a (meth) acryloyl group and an N-vinyl compound in which a vinyl group is directly bonded to a nitrogen atom can be used. When a compound having a radical polymerizable functional group is further added, the peel strength immediately after light irradiation can be increased.

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

  The resin filler (resin fine powder) is preferably a true spherical filler that can be easily obtained by suspension polymerization of a monomer (for example, methyl methacrylate) or the like. Moreover, since a resin filler is suitably contained as a filler in the composition, a spherical crosslinked resin filler is preferable.

  As the resin filler, a urethane resin filler and an acrylic resin filler are preferable, and a urethane resin filler is more preferable in terms of good compatibility with the component (A).

  The average particle diameter of the resin filler is preferably 1 to 150 μm, and more preferably 2 to 30 μm. In this embodiment, the average particle diameter is a 50% cumulative particle diameter measured by a laser diffraction scattering method. If the average particle size is smaller than 1 μm, it may be difficult to disperse in the system. On the other hand, if it is larger than 150 μm, it tends to be clogged with an application nozzle.

  0.5-200 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for the compounding ratio of the resin filler, 1-50 mass parts is more preferable. A resin filler may be used independently or may use 2 or more types together. In addition, when using the compound which concerns on this embodiment for the use as which light-shielding property is requested | required, it is preferable that a resin filler contains a black resin filler. By using a black resin filler having an average particle diameter of 1 to 150 μm, good deep curability can be obtained even when a single wavelength LED lamp or the like is used, and excellent light shielding properties and deep curability are obtained. Can be achieved.

  The method for producing the photocurable adhesive according to the present embodiment is not particularly limited. For example, a predetermined amount of components (B) and (C) is blended, and if necessary, components (A) and / or It can be produced by blending other compounding substances and stirring with heat deaeration. The order of blending each component and other compounding substances is not particularly limited and can be determined as appropriate.

  The photocurable adhesive according to the present embodiment can be a one-component type or a two-component type as required, but can be suitably used particularly as a one-component type.

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

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

  The photocurable adhesive curing method according to the present embodiment is, for example, as follows. First, a photocurable adhesive containing a thermoplastic resin, a photolatent curing catalyst, an organic polymer having a crosslinkable silicon group, and / or other compounding substances as necessary is prepared (preparation step). Next, the photocurable adhesive is heated to 50 ° C. or higher (heating step). And the heated photocurable adhesive agent is apply | coated to a predetermined to-be-adhered body (application | coating process). Subsequently, the photocurable adhesive applied to the adherend is cured by irradiating light (curing step). Thereby, the photocurable adhesive which concerns on this Embodiment hardens | cures.

Further, in the heating step, the heating temperature may be 50 ° C. or more and less than 50 ° C. as long as the viscosity of the photocurable adhesive is within a predetermined viscosity range by heating. The viscosity range determined in advance is preferably 0.1 to 1,000 Pa · s, more preferably 0.1 to 500 Pa · s when the photocurable adhesive is discharged. The viscosity can be measured using a rheometer that can measure the viscosity while heating. As the viscosity value in the present embodiment, a value measured using a BROOKFIELD, RHEOMETER, RST, shear rate: 20 s ⁻¹ , gap: 0.175 mm1, plate: parallel plate (φ: 25 mm) is used.

  When using the photocurable adhesive according to the present embodiment, there are no particular restrictions on the method of application to the adherend, but there are application methods such as screen printing, stencil printing, roll printing, die coater, spray coating, and spin coating. Preferably used. The thinner the coating thickness on the adherend, the easier it is to cure, and it is 500 μm or less, preferably 200 μm or less.

  In addition, since the photocurable adhesive according to the present embodiment has high thermal stability, it can be used for hot melt or warm melt. For example, the photocurable adhesive according to the present embodiment can be applied to a predetermined adherend using a hot melt dispenser, a hot melt gun, or a dispenser equipped with a temperature control unit. Moreover, after apply | coating a photocurable adhesive to a 1st to-be-adhered body, an active energy ray is irradiated to a photocurable adhesive, and the 2nd in the position which pinches | interposes the photocurable adhesive with which the active energy ray was irradiated. The adherend can be bonded to the first adherend. In addition, after irradiating the photocurable adhesive applied to the first adherend with active energy rays, the first adherend is applied to the second adherend even when the photocurable adhesive is uncured. It can also be pasted together. Further, after irradiating the photocurable adhesive applied to the first adherend with active energy rays, the photocurable adhesive is cured, and then the first adherend is attached to the second adherend. It can also be combined.

  Hot melt or warm melt using the photocurable adhesive according to the present embodiment can apply the photocurable adhesive to a predetermined adherend, so various adhesive tapes and labels, for portable electronic devices, for automobiles, For automotive interiors, OA, home appliances, construction / building materials, electronic parts, panels, applications that require rework or repair, protection, moisture prevention, 3D object formation by stereolithography, coating, bonding It can be suitably used for applications that sometimes require the application shape to be maintained, for bonding image display devices such as televisions, and for applications that require temporary fixability. In particular, it is suitable when an image display unit such as a portable electronic device is attached to a housing. Since the photocurable adhesive which concerns on this embodiment has high bonding intensity | strength, it can narrow a bonding location. Moreover, even if a bonding location is narrow, since it has strong adhesiveness, it is excellent also in waterproofness. Generally, after joining the image display unit and the housing, the quality of the electronic device is determined. In this pass / fail judgment, in the case of a defect, it is preferable from the viewpoint of cost that the image display unit is detached from the housing to repair or replace the defective product. Therefore, when the photocurable adhesive according to the present embodiment is used, it can be easily reworked by heating or the like, so that the expensive image display unit and the housing can be collected and reused.

  The photocurable adhesive according to this embodiment can be suitably used for various products such as electronic circuits, electronic components, building materials, automobiles, and the like.

  The photocurable adhesive according to this embodiment can be applied to the surface of a predetermined adherend. Moreover, the photocurable adhesive which concerns on this embodiment can be used for formation of the adhesive layer which comprises the adhesive tape which can be used for fixation of various members. As an adhesive tape, for example, a nonwoven fabric substrate, a foam substrate, and / or an adhesive tape having an adhesive layer on one or both sides, such as a resin film substrate, and a substrate-less material composed only of an adhesive layer An adhesive tape etc. are mentioned. When using a photocurable adhesive as an adhesive tape provided with an adhesive layer on one or both sides of the substrate, the thickness of the adhesive layer is preferably 10 μm to 150 μm, and more preferably 20 μm to 100 μm. . Moreover, when using a photocurable adhesive as a base material-less adhesive tape, it is preferable that the thickness of the adhesive layer formed from a photocurable adhesive is 10 micrometers-300 micrometers, and is 20 micrometers-250 micrometers. It is more preferable.

  The photocurable adhesive according to the present embodiment can be applied to the surface of a predetermined adherend by heating with a drum melter or the like to reduce the viscosity. Moreover, the adhesive tape which concerns on this embodiment is provided with the base material and the adhesive layer which is provided in the surface of a base material and is comprised from a photocurable adhesive agent. The pressure-sensitive adhesive layer can be produced by applying a photocurable adhesive on one side or both sides of a substrate using a roll coater, a die coater, or the like, and drying by UV irradiation. The pressure-sensitive adhesive tape is preliminarily coated with a photo-curable adhesive on the surface of the release liner using a roll coater, etc., and dried by UV irradiation to form a pressure-sensitive adhesive layer. It can be manufactured by a transfer method in which the substrate is bonded to one side or both sides. Further, the baseless pressure-sensitive adhesive tape can be produced by applying a photocurable adhesive to the surface of the release liner in advance using a roll coater or the like, and drying by UV irradiation.

  Examples of the base material constituting the adhesive tape include resin base materials such as polyester films, polyethylene films, polypropylene films, plastic films such as polyvinyl chloride films, non-woven base materials, foam base materials, cloths, and papers. It is done. As the resin base material, a resin base material subjected to corona treatment, anchor coat treatment, or the like can be used from the viewpoint of improving the anchoring effect of the pressure-sensitive adhesive layer formed from the photocurable adhesive.

  The thickness of the substrate is more preferably 1 μm to 500 μm from the viewpoint of providing the effect of imparting excellent tape workability and excellent followability to the adherend. Moreover, the adhesive tape may have another layer as needed other than a base material and an adhesive layer. Other layers include, for example, a laminate layer such as a polyester film, a light shielding layer, a light reflecting layer, a metal layer, etc. from the viewpoint of imparting dimensional stability, good tensile strength, and / or reworkability of the adhesive tape. The heat conductive layer can be mentioned.

  The release liner is not particularly limited as long as it can be easily removed from the pressure-sensitive adhesive layer. For example, a resin film (for example, polyester such as PET) having a release treatment applied to the surface using a fluorine compound, silicone, or the like. Film) or the like.

  The pressure-sensitive adhesive tape according to the present embodiment can be used for affixing the tape to a predetermined adherend. For example, various pressure-sensitive adhesive tapes / labels, portable electronic devices, automobiles, automobile interiors, OA It can be suitably used for various products such as home appliances, home appliances, construction / building materials, and electronic parts.

  The photocurable adhesive according to this embodiment will be described more specifically with reference to the following examples.

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

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

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

(Synthesis Example 2) Synthesis of (meth) acrylic polymer B1 having a silyl group having a trimethoxysilyl group Methyl methacrylate 70.00 g, 2-ethylhexyl methacrylate 30.00 g, 3-methacryloxypropyltrimethoxysilane 12.00 g , And titanocene diclyde 0.10 g as a metal catalyst, 8.60 g of 3-mercaptopropyltrimethoxysilane, and 20.00 g of a benzoquinone solution (95% THF solution) as a polymerization terminator, Synthesis Example 4 of WO2015-088021 According to the method, a (meth) acrylic polymer B1 having a trimethoxysilyl group was obtained. The (meth) acrylic polymer A2 had a peak top molecular weight of 4,000 and a molecular weight distribution of 2.4. ^The number of trimethoxysilyl groups contained by ¹ H-NMR measurement was 2.00 per molecule.

(Synthesis Example 3) Synthesis of fluorinated polymer C1 Polyoxypropylene diol having a molecular weight of about 2,000 is used as an initiator, and polyoxypropylene diol is obtained by reacting propylene oxide in the presence of a zinc hexacyanocobaltate-glyme complex catalyst. It was. According to the method of Synthesis Example 2 of WO2015-088021, a polyoxyalkylene polymer having an allyl group at the end of the obtained polyoxypropylene diol was obtained. The polyoxyalkylene polymer having an allyl group at the terminal is reacted with methyldimethoxysilane, which is a silicon hydride compound, by adding a platinum vinylsiloxane complex isopropanol solution, and the polyoxyalkylene having a methyldimethoxysilyl group at the terminal is reacted. A polymer A3 was obtained.
As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A3 having a methyldimethoxysilyl group by GPC, the peak top molecular weight was 15000 and the molecular weight distribution was 1.3. ^{According to 1} H-NMR measurement, the number of terminal methyldimethoxysilyl groups was 1.7 per molecule.

Next, 2.4 g of BF ₃ diethyl ether complex, 1.6 g of dehydrated methanol, 100 g of polymer A3, and 5 g of toluene, and a polyoxy having a fluorosilyl group at the terminal according to the method of Synthesis Example 4 of WO2015-088021 An alkylene polymer (hereinafter referred to as fluorinated polymer C1) was obtained. When the ¹ H-NMR spectrum of the obtained fluorinated polymer C1 was measured, the peak (m, 0.63 ppm) corresponding to silylmethylene (—CH ₂ —Si) of the polymer as a raw material disappeared, and the low magnetic field A broad peak appeared on the side (0.7 ppm to).

(Synthesis example 4) Synthesis | combination of the crosslinkable silicon group containing compound E1 which produces | generates an amino group by light 15.2-part 2-nitrobenzyl alcohol and 344 parts toluene were added to the flask, and it recirculate | refluxed at about 113 degreeC for 60 minutes. Thereafter, 20.5 parts of 3-isocyanatopropyltrimethoxysilane was added dropwise and stirred for 5 hours to produce a compound (a crosslinkable silicon group-containing compound that generates an amino group by light represented by the following formula (9). Referred to as generating compound E1). As a result of IR spectrum measurement of the photoaminosilane generating compound E1, no —N═C═O bond was detected.

Example 1
Into the flask, (A) an organic polymer having a crosslinkable silicon group and (B) a thermoplastic resin were added at a blending ratio shown in Table 1, and the mixture was stirred under reduced pressure at 120 ° C. to dissolve the thermoplastic resin. Thereafter, (C) a silicon compound having a Si—F bond and (D) a photobase generator were added, and the mixture was stirred under reduced pressure to obtain a photocurable adhesive according to Example 1. The characteristics of the obtained composition were evaluated by the following methods. The evaluation results are shown in Table 1. Moreover, what was hardened | cured by light irradiation in the sample which evaluates sclerosis | hardenability after light irradiation had adhesiveness which can be used as a photocurable adhesive agent.

In Table 1, the compounding amount of each compounding substance is indicated by g, and details of other compounding substances are as follows.
(Component A: Crosslinkable silicon group-containing organic polymer)
* 1 A1 Polyoxyalkylene polymer: Polymer A1 synthesized in Synthesis Example 1
(B component: thermoplastic resin)
* 2 B1 (meth) acrylic polymer: (meth) acrylic polymer B1 having a silyl group synthesized in Synthesis Example 2
* 3 B2 Terpene phenol resin: Trade name “YS Polystar T130”, manufactured by Yasuhara Chemical Co., Ltd. (C component: silicon compound having Si—F bond)
* 4 C1 fluorinated polymer: fluorinated polymer C1 synthesized in Synthesis Example 3
(D component: photobase generator)
* 5 Photobase generator D1: 4 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, trade name “IRGACURE 379EG” 50% PC solution, manufactured by BASF (D 'component: (C) component and other silanol condensation reaction accelerating catalysts excluding component (D))
* 6 D'1: Boron trifluoride complex: Boron trifluoride monoethylamine 10% PC solution * 7 D'2: Tertiary amine: 1,8-diazabicyclo (5.4.0) undecene-7, product Name “DBU”, San Apro Co., Ltd. * 8 D′ 3: Titanium alkoxide: Titanium tetrabutoxide, Tokyo Chemical Industry Co., Ltd. * 9 D′ 4: Aluminum chelate: Trade name “Aluminum Chelate D”, Kawaken Fine Chemical Co., Ltd. * 10 D'5: Tin catalyst: Trade name "Neostan U-100", manufactured by Nitto Kasei Kogyo Co., Ltd. (E component: photoaminosilane generator)
* 11 E1: Photoaminosilane generator: Photoaminosilane generating compound E1 synthesized in Synthesis Example 4

1) Stability during heating (heating stability test when UV is not irradiated)
A photocurable adhesive is poured into a cylindrical container having a diameter of 100 mm and a height of 1 mm so that the thickness is 1 mm, and the state of the photocurable adhesive is touched with a finger every 5 minutes in an environment of 100 ° C. in a dark room. It was confirmed. A case where the deposit remains on the finger after touching for 5 hours or longer (that is, when the photocurable adhesive exhibits a liquid state). The adhesive was gel or solid). In addition, in the column of the heating stability test at the time of UV non-irradiation in Table 1, the heating duration time when the test result is obtained is shown in the upper row, and the test result is shown in the lower row. For example, in Example 1, the photocurable adhesive remains liquid even after heating at 100 ° C. for 5 hours, whereas in Comparative Example 1, the composition gelled by heating at 100 ° C. for 40 minutes. Show.

2) Surface Curability Test A photocurable adhesive was applied on a PET film so as to have a thickness of 200 μm, and UV irradiation [irradiation conditions: UV-LED 365 nm, illuminance: 1000 mW / cm ² , integrated light quantity: 3000 mJ / cm ² Immediately after that, the time until the surface was cured by finger touch was measured every minute in an environment of 23 ° C. and 50% RH in a dark room. About the sample of Comparative Examples 1-5 which mix | blended D 'component, after application | coating, in the environment of 23 degreeC 50% RH under dark room, the time until the surface hardens | cures with a finger touch every minute was measured. . In the column of the surface curability test in Table 1, the time until the photocurable adhesive is cured is shown in the upper part, and the evaluation result is shown in the lower part. When the surface hardening time was less than 1 hour, it was evaluated as “◯”, and when it was 1 hour or more, it was evaluated as “x”.

(Comparative Examples 1-7)
A pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 1, and the characteristics were evaluated. The results are shown in Table 1.

  As shown in Table 1, the photo-curing adhesives according to the examples do not proceed with curing even when heated to a high temperature, that is, they are rapidly cross-linked by light irradiation despite excellent stability during heating. Was shown to progress.

  While the embodiments and examples of the present invention have been described above, the embodiments and examples described above do not limit the invention according to the claims. It should be noted that not all combinations of features described in the embodiments and examples are necessarily essential to the means for solving the problems of the invention.

Claims (13)

A heating step of heating a thermoplastic resin and a photocurable adhesive containing a photolatent curing catalyst to 50 ° C. or higher;
An application step of applying the heated photocurable adhesive to an adherend;
A curing method of a photocurable adhesive comprising: a curing step of irradiating and curing the photocurable adhesive applied to the adherend.   The method for curing a photocurable adhesive according to claim 1, wherein the photocurable adhesive further contains an organic polymer having a crosslinkable silicon group.   The photolatent curing catalyst includes at least one compound selected from the group consisting of a silicon compound having a Si-F bond used together with a photolatent compound and a photobase generator. Curing method of photo-curable adhesive.   The said photocurable adhesive agent further contains the crosslinkable silicon group containing compound which produces | generates 1 or more types of amino groups selected from the group which consists of a primary amino group and a secondary amino group with light. The hardening method of the photocurable adhesive agent of any one of -3. A heating step of heating a thermoplastic resin and a photocurable adhesive containing a photolatent curing catalyst until the viscosity of the photocurable adhesive becomes 0.1 to 1,000 Pa · s;
An application step of applying the heated photocurable adhesive to an adherend;
A curing method of a photocurable adhesive comprising: a curing step of irradiating and curing the photocurable adhesive applied to the adherend.   The method for curing a photocurable adhesive according to claim 5, wherein the photocurable adhesive further contains an organic polymer having a crosslinkable silicon group.   Hardened | cured material of the photocurable adhesive obtained by the hardening method of the photocurable adhesive of any one of Claims 1-6. A thermoplastic resin;
A photocurable adhesive used for heat application containing a photolatent curing catalyst.   The photocurable adhesive according to claim 8, further comprising an organic polymer having a crosslinkable silicon group.   10. The photolatent curing catalyst includes at least one compound selected from the group consisting of a silicon compound having a Si-F bond used together with a photolatent compound, and a photobase generator. Light curable adhesive.   The organic polymer having a crosslinkable silicon group is a polymer having a crosslinkable silicon group and a photoradically polymerizable vinyl group in the molecule (excluding those having a Si-F bond), and the molecule The polymer according to claim 9 or 10, wherein the polymer is one or more polymers selected from the group consisting of organic polymers having a crosslinkable silicon group other than a polymer having a crosslinkable silicon group and a radically polymerizable vinyl group. The photocurable adhesive of description.   The crosslinkable silicon group-containing compound that further generates one or more amino groups selected from the group consisting of a primary amino group and a secondary amino group by light is further contained. The photocurable adhesive of description.   The product formed using the photocurable adhesive agent of any one of Claims 8-12.