JP2001172514A - Photocrosslinkable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocrosslinkable composition excellent in storage stability and suitably used as an adhesive or a sealing agent, and an adhesive or a sealing agent using the composition. SOLUTION: The compound (A) having two or more hydrolyzable silyl groups in one molecule and the compound (A) by light irradiation
A photo-crosslinkable composition containing a compound (B) for cross-linking, and an adhesive and a sealing agent using the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photocrosslinkable composition, and more particularly to an adhesive and a sealing material using the photocrosslinkable composition.

[0002]

2. Description of the Related Art Curable compositions comprising a compound having a hydrolyzable silyl group such as an alkoxysilyl group have been known, and are used for adhesives and the like. For example, JP-A-56-67366 discloses a curable composition containing a compound having a hydrolyzable silyl group and a specific metal compound, and the metal compound prevents a cross-linking reaction caused by moisture in the air. Promoted. Further, organometallic compounds such as organotin and organotitanium are disclosed as compounds having a catalytic action.

[0003] The above composition is a composition in which a reaction is promoted by a specific metal compound and is cured by moisture in the air, and is used as an adhesive or a sealing material. However, because of the presence of certain metal compounds in the composition, they are easily cured by moisture in the air. Therefore, it is necessary to take measures to block moisture during storage, and it is necessary to store in a container or the like that requires airtightness. In use, it is necessary to take measures such as shielding from moisture as much as possible, and there has been a demand for improvement in storage stability.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photocrosslinkable composition which has excellent storage stability and is suitably used for adhesives and sealing materials. Still another object of the present invention is to provide an adhesive and a sealing material using the photocrosslinkable composition.

[0005]

According to the first aspect of the present invention,
A photocrosslinkable composition comprising a compound (A) having two or more hydrolyzable silyl groups in one molecule and a compound (B) that crosslinks the compound (A) by light irradiation.

According to a second aspect of the present invention, the compound (A) having a hydrolyzable silyl group is a polymer having a hydrolyzable silyl group at a terminal or a side chain in a polymer structure. The composition is an acidic composition.

The invention according to claim 3 is characterized in that the compound (B) is
The photocrosslinkable composition according to claim 1 or 2, which is a compound that generates an acid or a base when irradiated with light.

A fourth aspect of the present invention is an adhesive composition using the photocrosslinkable composition according to any one of the first to third aspects.

The invention according to claim 5 is a sealing material composition using the photocrosslinkable composition according to any one of claims 1 to 3.

The hydrolyzable silyl group of the present invention is not particularly limited as long as it is a silyl group that causes a hydrolysis reaction. For example, a silyl group in which an alkoxy group is bonded to a silicon element, and an oxime group is bonded to a silicon element. These include a silyl group, a silyl group in which an alkenyloxy group is bonded to a silicon element, a silyl group in which an acetoxy group is bonded to a silicon element, and a silyl group in which a halogen group such as chlorine, bromine, or iodine is bonded to a silicon element. Among the decomposable silyl groups, an alkoxysilyl group to which an alkoxy group is bonded is preferably used in terms of storage stability, economy and the like. Further, two or more different types of hydrolyzable silyl groups may be used in combination.

Here, the alkoxysilyl group means a monoalkoxysilyl group, a dialkoxysilyl group or a trialkoxysilyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, a tert-butoxy group, a phenoxy group and a benzyloxy group. In the case of a dialkoxysilyl group or trialkoxysilyl group, the same alkoxy group may be used, or different alkoxy groups may be combined.

The compound (A) having a hydrolyzable silyl group is not particularly limited as long as it has two or more hydrolyzable silyl groups in one molecule. A polymer having at least two or more hydrolyzable silyl groups in one molecule is preferably used in order to easily achieve a balance between cohesive strength and adhesiveness after curing. Examples of the polymer used include, for example, a polyether having at least two or more hydrolyzable silyl groups in one molecule, a polyether having an alkylene glycol such as propylene glycol, ethylene glycol, or butylene glycol as a monomer unit, and a polyester having an ester bond. And polymers having an amide bond, polycarbonate having a carbonate bond, polymers such as polymethacrylate, polyacrylate, polystyrene, and polyolefin. These polymers may be used alone or in combination of two or more. Further, a copolymer having the above polymer structure may be used.

The bonding position of the alkoxysilyl group to the polymer may be bonded to the terminal of the polymer or to a side chain of the polymer. Further, it may be bonded to both the polymer terminal and the side chain. The molecular weight of these polymers is not particularly limited, but is preferably 4,000 to 30,000, particularly preferably 10,000 to 30,000, from the viewpoint of workability, physical properties after curing, and the like. The molecular weight distribution is preferably narrow in view of workability, physical properties after curing, and the like, and the ratio of Mw / Mn is preferably 1.6 or less.

Examples of the compound (A) include, for example, MS Polymers S-203 and S-30 manufactured by Kaneka Chemical Industry Co., Ltd.
3, S-903, Cyril SAT-200, MA-40
3. MA-447, EXETER ES manufactured by Asahi Glass Co., Ltd.
Commercially available compounds such as S-2410, ESS-2420, ESS-3630 can be used.

The compound (B) for crosslinking the compound (A) by light irradiation is not particularly limited as long as it is activated by light irradiation and crosslinks the compound (A). Specific examples include, for example, a photoacid generator, a photobase generator, a photocationic catalyst, and the like, and a photoacid generator and a photobase generator are preferably used. These compounds may be used alone or as long as they do not inhibit the effects of the present invention.
Species or more may be used in appropriate combination.

The photosensitive wavelength of the compound (B) is not particularly limited, but is preferably at least 300 nm.
A compound sensitive to light containing a wavelength component of 800 nm is preferably used. When a compound that is sensitive only to light having a wavelength shorter than 300 nm is used, the compound (A) is promptly used.
However, when the composition of the present invention is applied with a large thickness, only the surface increases the cohesion, and the cohesion does not uniformly appear throughout the composition, or the light irradiation surface wets. Properties are remarkably reduced, or a light source for irradiating light is limited. On the other hand, when the compound (B) is exposed only to light having a wavelength exceeding 800 nm, the compound (B) is easily decomposed even by low energy, that is, heat energy, and it is difficult to ensure storage stability. There is.

Examples of the photoacid generator include nitrobenzyl esters, sulfones, phosphates, N
-Hydroxyimidosulfonates, phenolsulfonates, diazonaphthoquinones, iminosulfonates and the like. Specific examples of these are, for example, TAZ-100, 101, 102, -1
04, 106, 113, 114, MBZ-101, 10
3, DNB-101, NB-103, SI-100,
Commercially available products such as 101, NAI-100 and 101 (manufactured by Midori Kagaku) can be used.

Examples of the photobase generator include cobalt (III) amine salts, o-acyl oximes, N-
(Benzyloxy) carbonylamines and the like. Specific examples of these include, for example, NBC-
Commercially available products such as 101, TPS-OH (manufactured by Midori Kagaku) can be used.

The photocationic catalyst is, for example, a compound which is activated by light and polymerizes or cures a compound containing a cationically polymerizable group. Examples thereof include iron-allene complex compounds, aromatic diazonium salts and aromatic iodonium salts. , Aromatic sulfonium salts, pyridiniums, aluminum complexes / silanol salts and the like.
Of these, compounds having a low thermal catalytic activity at around 20 to 80 ° C are preferred from the viewpoint of storage stability. Specifically, for example, Irgacure 261 (manufactured by Ciba Geigy), Optmer SP-150, 151, 170, 171 (manufactured by Asahi Denka Kogyo), UVE-1014 (manufactured by General Electronics), CD-1012 (manufactured by Sartomer) San-Aid SI-60L, 80L, 100L (manufactured by Sanshin Chemical Industry Co., Ltd.), CI-2064, 2639, 2624, 248
1 (Nippon Soda Co., Ltd.), RHODORSIL PHOTOINITIATOR 20
74 (Rhone Poulin), UVI-6990 (Union Carbide), BBI-103, MPI-
103, TPS-103, MDS-103, DTS-1
03, NAT-103, NDS-103 (manufactured by Midori Kagaku) and the like can be used.

The compounding ratio of the compound (A) and the compound (B) in the composition of the present invention is not particularly limited as long as the compound (A) is cross-linked by light irradiation. Compound (B) 0.001
-30 parts by weight are preferred. When compound (B) is 0.001
If the amount is less than part by weight, the crosslinking speed of the compound (A) may be significantly reduced or the degree of crosslinking of the cured product may be lowered, and the material may not be practically practical even if excessive light energy is irradiated. On the other hand, if it exceeds 30 parts by weight, the curing speed becomes too fast, and the physical properties after curing may decrease, or it may be difficult to obtain a sufficient adhesive strength.

The composition of the present invention may contain, if necessary, a sensitizer for improving the photosensitivity of the compound (B), a thickener for adjusting the viscosity characteristics of the composition, a thixotropic material,
Various additives such as a physical property modifier, a crosslinking accelerator, a bulking agent, a reinforcing agent, a plasticizer, a colorant, and a flame retardant for improving physical properties after curing may be added.

Examples of the sensitizer include anthracene, perylene, coronene, tetracene, benzanthracene, phenothiazine, flavin, acridine, ketocoumarin, a thioxanthone derivative, benzophenone, acetophenone, 2-chlorothioxanthone, and 2,4-dimethylthio. Xanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone and the like can be mentioned. These sensitizers may be used in combination of two or more.

As the above thickener, for example, compound (A)
It is selected from high molecular compounds having good compatibility with, and is appropriately selected according to the compound (A) used. For example, acrylic polymers, methacrylic polymers, polyvinyl alcohol derivatives, polyvinyl acetate, polystyrene derivatives, polyesters, polyethers, polyisobutene, polyolefins, polyalkylene oxides, polyurethanes, polyamides, natural rubber, polybutadiene , Polyisoprene, NBR, SBS, SIS, SEBS, hydrogenated N
BR, hydrogenated SBS, hydrogenated SIS, hydrogenated SEBS, and the like. Further, a copolymer or derivative of these polymer compounds may be used. These polymer compounds may be used alone or in combination of two or more.

The thixotropic agent is appropriately selected from substances which exhibit thixotropic properties when added to the composition. For example, colloidal silica, polyvinylpyrrolidone, hydrophobized calcium carbonate, glass balloon, glass beads and the like can be mentioned. These are preferably those having a surface having a high affinity with the compound (A) in consideration of dispersibility, physical properties after curing, and the like.

Examples of the physical property modifier include various silane coupling agents, for example, vinyltrimethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyl Trimethoxysilane, diphenyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N -(2-aminoethyl) -3-aminopropyltriethoxysilane, N, N'-bis-
[3- (Trimethoxysilyl) propyl] ethylenediamine, N, N'-bis- [3- (triethoxysilyl)
Propyl] ethylenediamine, N, N'-bis- [3-
(Trimethoxysilyl) propyl] hexaethylenediamine, N, N'-bis- [3- (triethoxysilyl)
Propyl] hexaethylenediamine and the like, which may be used alone or in combination of two or more.

The crosslinking accelerator may be any compound which promotes crosslinking of the compound (A). Examples thereof include dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, and bis (dibutyltin laurate). ) Oxide, dibutyltin bisacetylacetonate, dibutyltin bis (monoester malate),
Tin compounds such as tin octylate, dibutyltin octoate and dioctyltin oxide; titanate compounds such as tetra-n-butoxytitanate and tetraisopropoxytitanate; amine salts such as dibutylamine-2-ethylhexoate; and other acidic compounds Examples thereof include a catalyst and a basic catalyst, which may be used alone or in combination of two or more.

As the above-mentioned extender, those which do not exhibit thixotropic properties when added to the composition according to the present invention can be suitably used. For example, talc, clay, calcium carbonate, magnesium carbonate, anhydrous silicon, hydrous silicon, Examples thereof include calcium silicate, titanium dioxide, and carbon black, and these may be used alone or in combination of two or more.

Examples of the plasticizer include phosphoric esters such as tributyl phosphate and tricresyl phosphate; phthalic esters such as dioctyl phthalate; fatty acid monobasic esters such as glycerin monooleate; and adipine Examples thereof include fatty acid dibasic acid esters such as dioctyl acid, and polypropylene glycols, and these may be used alone or in combination of two or more. In addition, if necessary, an anti-sagging agent, an antioxidant, an anti-aging agent, an ultraviolet absorber, a solvent, a fragrance, a pigment, a dye, and the like may be added.

The light source used for light irradiation of the composition of the present invention is a light source capable of emitting light containing a wavelength component for activating the compound (B) or a sensitizer added for the purpose of improving photosensitivity. It is not particularly limited as long as it is present, and is appropriately selected depending on the compound (B) or the sensitizer. For example, low-pressure mercury lamps,
Medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, excimer lasers, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, sodium lamps, fluorescent lamps, sunlight and the like are used. Also,
Unwanted wavelength components may be reduced or removed using a filter or the like.

The above photocrosslinkable composition can be used for paints, inks, coating materials, surface protection materials, adhesives, sealing materials, surface treatment agents and the like. For example, when used as an adhesive composition, the adhesive composition is applied to one joining member, light is irradiated from the upper surface of the applied composition layer of the joining member, and then the other joining member is attached and joined. Is done. Alternatively, after the adhesive composition is irradiated with light, the composition is applied to a bonding member and bonded to each other. Alternatively, when at least one of the adherends is transparent, the adhesive composition is applied to one of the joining members, and then the other joining members are attached to each other, followed by light irradiation for joining.

When used as a sealing material composition, the above-mentioned sealing material composition is filled in a filling place,
It is constructed by irradiating light. In addition, after the sealing material composition is irradiated with light in advance, the sealing material composition is filled at the filling location.

[0032]

The present invention will be described below with reference to examples. However, the following examples are for illustrating the present invention, but not for limiting the present invention. Example 1 Compound (A) (MS polymer S-303, manufactured by Kaneka Corporation) in a 0.3 L beaker protected from light with aluminum foil
100 g, Compound (B) (ADEKA OPTOMER SP-17)
(0, manufactured by Asahi Denka Co., Ltd.) was stirred and mixed until uniform to prepare a photocrosslinkable composition.

The obtained composition was evaluated according to the following evaluation method.
The amount of the crosslinking component, the shear adhesive strength, and the storage stability were evaluated. The cross-linking component amount is 76%, the shear adhesive strength is 0.49 MPa,
No increase in viscosity of the composition and generation of gel during storage could be confirmed. After filling the joints with the above composition, the joints were irradiated with light and cured at room temperature for 7 days. The state was observed and evaluated as a sealing material. The surface was tack-free and in a rubbery state, and was sufficiently adhered to the substrate.

Example 2 Compound (A) (MS polymer S-303, manufactured by Kaneka Corporation) in a 0.3 L beaker protected from light with aluminum foil.
100 g and 5 g of the compound (B) (NBC-101, manufactured by Midori Kagaku Co., Ltd.) were stirred until uniform, and then the sensitizer (N
-Phenylglycine) in an amount of 2 g to obtain a composition. The obtained composition was evaluated in the same manner as in Example 1. The cross-linking component amount is 46%, the shear adhesive strength is 0.2 MPa,
No increase in viscosity of the composition and generation of gel during storage could be confirmed. After filling the joints with the above composition, the joints were irradiated with light and cured at room temperature for 7 days. The state was observed and evaluated as a sealing material. The surface was tack-free and in a rubbery state, and was sufficiently adhered to the substrate. Met.

Comparative Example 1 The procedure of Example 1 was repeated except that the compound (B) was not used. No crosslinkable component could be detected.

[Evaluation Method] (Amount of Crosslinking Component) The obtained composition was coated on a release-treated glass plate so as to have a thickness of 100 μm, and irradiated with ultraviolet light (at 365 nm) using a high-pressure mercury lamp. 1500mJ / cm
After the irradiation of ² ), the mixture was cured for 7 days in a dark place at a temperature of 23 ° C. and a humidity of 65 RH%. Take a certain amount of sample from the living organism,
After immersion in tetrahydrofuran (THF) for 1 day at room temperature, the mixture was shaken for 5 hours, and the amount of gel component (THF-insoluble component) was determined. The gel fraction in the sample was taken as the amount of the crosslinking component. (Adhesive force) Slate-made adherend (25 mm x 35 mm)
On top, the composition of the present invention is 25 mm × 25 mm × 0.1 m
m to obtain an object to be coated. Ultraviolet rays (1,500 mJ / 365 nm) were applied to the object using a high-pressure mercury lamp.
cm ² ) and then adhere the adherend. After bonding, 7 ° C in a dark place at a temperature of 23 ° C and a humidity of 65 RH%
After curing for days, an evaluation test sample was obtained. With respect to the obtained sample, the compression shear adhesion was evaluated by a compression test (crosshead speed: 10 mm / min) according to JIS K 6852. (Storage stability) After the obtained composition was allowed to stand at 24 ° C. for 1 month under light shielding, a change in viscosity and a visual observation of gel generation were performed.

[0037]

According to the first aspect of the present invention, two molecules per molecule are provided.
Since it contains the compound (A) having at least two hydrolyzable silyl groups and the compound (B) which crosslinks the compound (A) by irradiation with light, the reaction does not proceed while light is blocked, and the storage is good. It is a photocrosslinkable composition that exhibits properties and can be irradiated with light to promote the reaction and obtain a good crosslinked product. According to the second aspect of the present invention, the compound (A) having a hydrolyzable silyl group is a polymer having a hydrolyzable silyl group at a terminal or a side chain in a polymer structure.
It is a photocrosslinkable composition that can more reliably exert the effect of (1). According to the third aspect of the present invention, since the compound (B) is a compound that generates an acid or a base when irradiated with light, the light capable of more reliably achieving the effects of the first or second aspect is obtained. It is a crosslinkable composition. Since the present invention according to claim 4 uses the photocrosslinkable composition according to any one of claims 1 to 3, the photocrosslinkable composition has excellent storage stability, curability, impact resistance, and creep resistance. Adhesive. Since the present invention according to claim 5 uses the photocrosslinkable composition according to any one of claims 1 to 3, storage stability, curability,
A photo-crosslinkable sealing material with excellent impact resistance and adhesiveness.

Continued on the front page F-term (reference) 4H017 AA31 AB15 AC05 AC08 AC16 AC17 4J002 CP051 CP081 CP091 CP121 FD206 GH00 GH01 GJ01 GJ02 4J040 DA001 DB031 DF041 DF051 ED161 EE021 EG001 EL021 GA31 HB21 HB30 HD08 HD16 HD13

Claims (5)

[Claims] 1. A compound (A) having two or more hydrolyzable silyl groups in one molecule and a compound (A) upon irradiation with light
A photocrosslinkable composition comprising a compound (B) that crosslinks the compound. 2. The photocrosslinkable compound according to claim 1, wherein the compound (A) having a hydrolyzable silyl group is a polymer having a hydrolyzable silyl group at a terminal or a side chain in the polymer structure. Composition. 3. The photocrosslinkable composition according to claim 1, wherein the compound (B) is a compound that generates an acid or a base when irradiated with light. 4. An adhesive composition comprising the photocrosslinkable composition according to claim 1. 5. A sealing material composition comprising the photocrosslinkable composition according to claim 1.