JP2023038678A - Curable composition - Google Patents

Abstract

To provide a curable composition that excels in the curability and curing speed of an unexposed portion.SOLUTION: A curable composition according to one aspect of the present invention contains a (meth)acrylate polymer (I) having one or more crosslinkable silyl groups on average for one molecule, and a naphthoquinone azide compound (II).SELECTED DRAWING: None

Description

The present invention relates to curable compositions.

In recent years, curable compositions used in the fields of coating agents, adhesives, resists, electrode-forming materials, etc., are characterized by rapid curing, reduction of damage to adherends (damage due to heat generation, etc.), light There are advantages such as a reduction in the introduction cost of the irradiation equipment and the possibility of spot curing on site. However, the curable composition that is cured by light irradiation has a problem of insufficient curability in dark areas where light is not irradiated.

Therefore, in order to solve the above problems, curable compositions having excellent curability have been developed. For example, Patent Literature 1 discloses a curable composition comprising an organic polymer having an average of at least one terminal crosslinkable silyl group, and a photoacid generator. Further, Patent Document 2 discloses a curable composition containing an organic polymer having two or more hydrolyzable silyl groups in one molecule, a compound that generates an acid or base upon irradiation with light, and a silanol-containing compound. It is

It should be noted that Patent Document 2 specifically discusses a polyisobutylene-based polymer having a hydrolyzable silyl group. A polyisobutylene-based polymer differs from an acrylic polymer in the main chain structure of the polymer, and therefore the properties of the polymer are also greatly different from those of the acrylic polymer. Therefore, it is difficult for those skilled in the art to immediately apply the technology disclosed in Patent Document 2 to Patent Document 1.

JP 2011-208073 A JP 2015-021103 A

However, the prior art as described above has room for further improvement with respect to the curability of the curable composition located in the unexposed area (the area not irradiated with light) and its curing speed.

An object of one aspect of the present invention is to provide a curable composition that is excellent in curability and curing speed in unexposed areas.

The curable composition according to one aspect of the present invention is
a (meth)acrylic ester-based polymer (I) having an average of one or more crosslinkable silyl groups per molecule;
a naphthoquinone azide compound (II);
including.

An aspect of the present invention provides a curable composition that exhibits excellent curability and curing speed in unexposed areas.

Examples of embodiments of the present invention will be described in detail below, but the present invention is not limited to these.

Unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more and B or less". As used herein, "(meth)acryl" means "acryl" and/or "methacryl".

[1. meth) acrylic acid ester polymer (I)]
[1.1. Main Chain of (Meth)Acrylic Acid Ester Polymer (I)]
The acrylic acid ester monomer constituting the main chain of the (meth)acrylic acid ester polymer (I) is not particularly limited. Examples of acrylic acid ester monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, Isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylate- n-heptyl, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, (meth)acrylic acid Phenyl, toluyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, ( 2-hydroxypropyl meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, γ-(methacryloyloxypropyl)trimethoxysilane, (meth)acrylic acid Ethylene oxide adducts of, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-per(meth)acrylate Fluoroethyl-2-perfluorobutylethyl, (meth)acrylic acid-2-perfluoroethyl, (meth)acrylic acid perfluoromethyl, (meth)acrylic acid diperfluoromethylmethyl, (meth)acrylic acid-2- Perfluoromethyl-2-perfluoroethylmethyl, (meth)acrylate-2-perfluorohexylethyl, (meth)acrylate-2-perfluorodecylethyl, (meth)acrylate-2-perfluorohexadecylethyl is mentioned. These monomers may be used alone, or may be used by copolymerizing a plurality of types.

The main chain of the (meth)acrylic acid ester polymer (I) preferably contains (meth)acrylic acid ester monomer units as a main component, and more preferably contains acrylic acid ester monomer units as a main component. The (meth)acrylic acid ester polymer (I) having such a main chain structure has excellent physical properties at low temperatures (flexibility, viscosity, elongation, etc.).

Here, in relation to the main chain of the polymer, the term “contains as a main component” means that 50 mol% or more (preferably 70 mol% or more, more preferably 90 mol% or more) of the monomer units constituting the main chain ) is occupied by a specific monomer. Therefore, "the main chain of the (meth)acrylic acid ester polymer (I) is mainly composed of (meth)acrylic acid ester monomer units" means that the main component of the (meth)acrylic acid ester polymer (I) is It means that 50 mol % or more (preferably 70 mol % or more, more preferably 90 mol % or more) of the chain is occupied by (meth)acrylate monomer units.

Among the above (meth)acrylic acid ester monomers, acrylic acid alkyl ester monomers are particularly preferred. Specific examples of acrylic acid alkyl ester monomers include ethyl acrylate, 2-methoxyethyl acrylate, stearyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and 2-methoxybutyl acrylate.

These monomers may be used alone, or may be used by copolymerizing a plurality of types. When multiple types are copolymerized, they may be randomly copolymerized or block copolymerized.

The molecular weight distribution of the (meth)acrylate polymer (I) is not particularly limited. The molecular weight distribution is preferably less than 1.8, more preferably 1.7 or less, even more preferably 1.6 or less, even more preferably 1.5 or less, and particularly preferably 1.4. or less, and most preferably 1.3 or less. (Meth)acrylic acid ester polymer (I) If the molecular weight distribution is too large, the viscosity of the polymer tends to increase, making it difficult to handle.

As used herein, molecular weight distribution means the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). The weight average molecular weight and number average molecular weight are values measured by gel permeation chromatography (GPC). In one embodiment, GPC measurements use chloroform as the mobile phase and a polystyrene gel column as the stationary phase. In one embodiment, the weight average molecular weight and number average molecular weight are determined as polystyrene equivalent values.

The number average molecular weight of the (meth)acrylate polymer (I) is not particularly limited. The lower limit of the number average molecular weight is preferably 500 or more, more preferably 1,000 or more, still more preferably 5,000, and particularly preferably 8,000. The upper limit of the number average molecular weight is preferably 1,000,000 or less, more preferably 100,000 or less, still more preferably 80,000 or less, and particularly preferably 50,000 or less. If the number average molecular weight is too low, the elongation and flexibility of the resulting cured product tend to be poor. If the number average molecular weight is too high, the polymer tends to become highly viscous and difficult to handle.

[1.2. Method for Synthesizing (Meth)Acrylic Acid Ester-Based Polymer (I)]
The method for synthesizing the (meth)acrylate polymer (I) is not particularly limited. From the viewpoint of versatility of monomers and ease of control, radical polymerization is preferred, and among radical polymerizations, controlled radical polymerization is more preferred. Controlled radical polymerization can be classified into "chain transfer agent method" and "living radical polymerization". Living radical polymerization is preferred because the molecular weight and molecular weight distribution of the resulting polymer can be easily controlled. Furthermore, among the living radical polymerizations, atom transfer radical polymerization is more preferable because the starting materials to be used are readily available and functional groups can be easily introduced to the ends of the polymer.

The above radical polymerization, controlled radical polymerization, chain transfer agent method, living radical polymerization and atom transfer radical polymerization are known polymerization methods. For details of these polymerization methods, see, for example, JP-A-2005-232419 and JP-A-2006-291073.

Atom transfer radical polymerization is briefly described below.

An organic halide or a sulfonyl halide compound is preferable as the initiator used in the atom transfer radical polymerization. Among organic halides, organic halides having a highly reactive carbon-halogen bond are particularly preferred. Examples of such organic halides include carbonyl compounds having a halogen at the α-position and compounds having a halogen at the benzylic position.

Preferred initiators are compounds having two or more initiation points (organic halides, sulfonyl halide compounds, etc.). When such a compound is used as the initiating site, a (meth)acrylic acid ester polymer having two or more alkenyl groups in one molecule can be obtained. By hydrosilylating this alkenyl group, a (meth)acrylic acid ester polymer (I) having an average of one or more crosslinkable silyl groups per molecule can be obtained.

The (meth)acrylate monomer used for atom transfer radical polymerization is not particularly limited. Any of the (meth)acrylate monomers exemplified above can be suitably used.

The transition metal complex used as the polymerization catalyst is not particularly limited. Preferred are metal complexes having an element of groups 7, 8, 9, 10 or 11 of the periodic table as the central metal. More preferred are transition metal complexes having zerovalent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel as a central metal. Particularly preferred are copper complexes. Examples of monovalent copper compounds used to form copper complexes include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous oxide, Cuprous chlorate is mentioned.

When a copper compound is used as a polymerization catalyst, polyamine as a ligand may be added in order to enhance catalytic activity. Examples of polyamines include 2,2′-bipyridyl or its derivatives, 1,10-phenanthroline or its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, hexamethyltris(2-aminoethyl)amine. is mentioned.

The polymerization reaction may proceed without solvent or in various solvents. The type of solvent used for polymerization is not particularly limited. Examples of solvents include solvents described in paragraph [0067] of JP-A-2005-232419. A solvent may be used independently and may use 2 or more types together. Polymerization may also proceed in an emulsion system or a system mediated by supercritical fluid _CO2 .

The polymerization temperature is not particularly limited. It is preferably from 0 to 200°C, more preferably from room temperature (eg, 20°C) to 150°C.

[1.3. Crosslinkable silyl group]
In one embodiment, the crosslinkable silyl group possessed by the (meth)acrylate polymer (I) is represented by the following general formula (1).
[Si(R ¹ ) _2-b (Y) _b O] _m -Si(R ² ) _3-a (Y) _a (1)

In formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R') ₃ Represents a triorganosiloxy group represented by the formula SiO—. When two or more of each of R ¹ or R ² are present, they may be the same or different. R' represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. Plural R's may be the same or different. Y represents a hydroxyl group or a hydrolyzable group. When two or more Y are present, they may be the same or different. a represents an integer of 0, 1, 2 or 3; b represents an integer of 0, 1, or 2; m represents an integer from 0 to 19; satisfies a+mb≧1.

Examples of hydrolyzable groups represented by Y include hydrogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amido groups, aminooxy groups, mercapto groups and alkenyloxy groups. Among these, an alkoxy group, an amido group, and an aminooxy group are preferred. An alkoxy group is more preferable in terms of moderately low hydrolyzability and ease of handling. The reactivity of the alkoxy group is higher as the number of carbon atoms is smaller. For example, the reactivity decreases in the order of methoxy group, ethoxy group, and propoxy group. The type of alkoxy group can be appropriately selected depending on the purpose and application.

One to three hydrolyzable groups and/or hydroxyl groups represented by Y can be bonded to one silicon atom. As for a and b in the above formula (1), it is preferable that the relationship 1≦(a+Σb)≦5 is established. When two or more hydrolyzable groups and/or hydroxyl groups are bonded to a crosslinkable silyl group, they may be the same or different. One or more silicon atoms form a crosslinkable silyl group. When taking a structure in which a plurality of silicon atoms are linked by a bond such as a siloxane bond, the total number of silicon atoms is preferably 20 or less.

The structure of the crosslinkable silyl group is preferably represented by the following general formula (2) because it is readily available.
Si(R ² ) _3-a (Y) _a (2)

In formula (2), R ² and Y are the same as in formula (1). a is an integer of 1 to 3; From the viewpoint of the curability of the curable composition and physical properties of cured particles, a is preferably 2 or 3.

As an example of such a crosslinkable silyl group, a crosslinkable silyl group where a=2 (such as a dimethoxy crosslinkable group) is well known. However, especially when a very fast cure rate is required (such as when used at low temperatures), the cure rate may be too slow with a crosslinkable silyl group where a=2. In addition, in order to obtain a flexible cured product using the (meth)acrylate polymer (I) having a crosslinkable silyl group where a = 2, it is necessary to reduce the crosslink density. However, stickiness (surface tack) may occur due to the reduction in cross-linking density. In such a case, it is preferable to employ a crosslinkable silyl group in which a=3.

A crosslinkable silyl group with a=3 (trimethoxy functional group) has a faster curing rate than a crosslinkable silyl group with a=2 (dimethoxy functional group, etc.). On the other hand, in terms of storage stability and mechanical properties (elongation, etc.), the crosslinkable silyl group where a=2 may be superior. Therefore, in order to balance curability and physical properties, a crosslinkable silyl group with a=2 and a crosslinkable silyl group with a=3 may be used in combination. In this case, a (meth)acrylic ester-based polymer (I) containing two or more types of crosslinkable silyl groups in one molecule may be used. The above (meth)acrylic acid ester polymer (I) may be used.

When the structure of Y is the same, the more a, the higher the reactivity of Y. Therefore, by variously selecting Y and a, the curability and mechanical properties of the cured product can be controlled. Y and a can be appropriately selected depending on the purpose and application.

The crosslinkable silyl group where a = 1 is chain-extended by mixing with other crosslinkable silyl group-containing polymers (polysiloxane-based polymer, polyoxypropylene-based polymer, polyisobutylene-based polymer, etc.). It can be used as an agent. By using such a (meth)acrylate polymer (I), the viscosity of the curable composition before curing can be reduced. In addition, by using such a (meth)acrylic acid ester polymer (I), the elongation at break of the cured product after curing can be improved, bleeding of the cured product can be reduced, and contamination of the surface can be reduced.

From the viewpoint of the curability of the curable composition and the physical properties of the cured product, the number of crosslinkable silyl groups contained in the (meth)acrylate polymer (I) is, on average, one per molecule. That's it. The lower limit of the number of crosslinkable silyl groups per molecule is preferably 1.1 or more, more preferably 1.2 or more. The upper limit of crosslinkable silyl groups per molecule is preferably 4.0 or less, more preferably 3.5 or less.

When the cured product is required to have properties as a rubber, at least one crosslinkable silyl group contained in the (meth)acrylic acid ester polymer (I) is preferably located at a molecular terminal. , are all located at the ends of the molecular chains. With such a molecular design, the molecular weight between cross-linking points can be increased. Therefore, the rubber elasticity of the cured product can be enhanced.

A method for synthesizing a (meth)acrylic acid ester polymer having a crosslinkable silyl group at the molecular chain end is disclosed, for example, in JP-B-03-014068, JP-B-04-055444, and JP-A-06-211922. ing. However, the method disclosed in these documents is a free radical polymerization using a chain transfer agent method. Therefore, the resulting polymer tends to have a large molecular weight distribution value (usually 2.0 or more), high viscosity, and difficulty in handling. In order to obtain a (meth)acrylic acid ester polymer (I) having a narrow molecular weight distribution, a low viscosity, and a high ratio of crosslinkable silyl groups at the molecular chain ends, living radical polymerization is preferably employed. .

[1.4. Method for introducing crosslinkable silyl group]
A known method can be used to introduce a crosslinkable silyl group into the (meth)acrylate polymer. Examples of such methods include those described in paragraphs [0083] to [0117] of JP-A-2007-302749. Among the methods described, from the viewpoint of ease of control, a hydrosilane compound having a crosslinkable silyl group is added to a (meth)acrylate polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst. The preferred method is to

A known method can be used to introduce an alkenyl group into the (meth)acrylate polymer. Since the introduction of alkenyl groups is easy to control, a (meth)acrylic acid ester polymer is synthesized by living radical polymerization, and at the end of the polymerization reaction or after the completion of the reaction of a predetermined proportion of monomers, alkenyl groups with low polymerizability is simple and preferable. Of course, after obtaining a (meth)acrylic acid ester-based polymer by living radical polymerization, the obtained polymer may be isolated from the polymerization system, and an alkenyl group may be introduced at the end by radically reacting a diene compound. good.

The alkenyl group possessed by the diene compound may be either a terminal alkenyl group or an internal alkenyl group. A terminal alkenyl group is preferred.

A terminal alkenyl group is a group represented by CH ₂ =C(R)-R'. In the formula, R is hydrogen or an organic group having 1 to 20 carbon atoms. R' is a monovalent or divalent organic group having 1 to 20 carbon atoms. R and R' may combine with each other to have a cyclic structure.

The internal alkenyl group is a group represented by R'-C(R)=C(R)-R'. In the formula, R is hydrogen or an organic group having 1 to 20 carbon atoms. R' is a monovalent or divalent organic group having 1 to 20 carbon atoms. Two R's may be the same or different. Two R's may be the same or different. Two of each of R and R' may be bonded together to form a cyclic structure.

The organic group having 1 to 20 carbon atoms represented by R is preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and hydrogen or A methyl group is more preferred. The monovalent or divalent organic group having 1 to 20 carbon atoms represented by R′ includes a monovalent or divalent alkyl group having 1 to 20 carbon atoms, and a monovalent or divalent organic group having 6 to 20 carbon atoms. An aryl group or a monovalent or divalent aralkyl group having 7 to 20 carbon atoms is preferred, and a methylene group, ethylene group or isopropylene group is more preferred. Two or more alkenyl groups contained in the diene compound may be the same or different. At least two alkenyl groups among the alkenyl groups contained in the diene compound may be conjugated.

Examples of diene compounds include isoprene, piperylene, butadiene, myrcene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene. Among these, 1,5-hexadiene, 1,7-octadiene and 1,9-decadiene are preferred.

When a diene compound having a large difference in reactivity between two alkenyl groups is used, the amount of the diene compound to be added may be an equivalent amount or a slight excess amount relative to the growing end of the polymer. When using a diene compound in which two alkenyl groups have the same level of reactivity, the amount of the diene compound added is preferably an excess amount relative to the growing ends of the polymer. An excess amount means preferably 1.5 times or more, more preferably 3 times or more, and still more preferably 5 times or more.

A hydrosilane compound having a crosslinkable silyl group is not particularly limited. In one embodiment, the hydrosilane compound is a compound represented by general formula (3) below.
H—[Si(R ³ ) _2-b (Y) _b O] _m —Si(R ⁴ ) _3-a (Y) _a (3)

In formula (3), R ³ and R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R') ₃ Represents a triorganosiloxy group represented by the formula SiO—. When two or more of each of ^R3 or ^R4 are present, they may be the same or different. R' represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. Plural R's may be the same or different. Y represents a hydroxyl group or a hydrolyzable group. When two or more Y are present, they may be the same or different. a represents an integer of 0, 1, 2 or 3; b represents an integer of 0, 1, or 2; m represents an integer from 0 to 19; satisfies a+mb≧1.

Examples of the hydrolyzable group represented by Y are the same as in formula (1).

Of the hydrosilane compounds represented by formula (3), compounds represented by the following general formula (4) are preferred because the compounds are readily available.
H—Si(R ⁴ ) _3-a (Y) _a (4)

In the formula, ^R4 and Y are the same as in formula (3). a is an integer of 1 to 3;

A transition metal catalyst is usually used when adding a hydrosilane compound having a crosslinkable silyl group to an alkenyl group. Examples of transition metal catalysts include simple platinum; platinum solid dispersed in a carrier (alumina, silica, carbon black, etc.); chloroplatinic acid; complexes of chloroplatinic acid with alcohols, aldehydes, ketones, etc.: platinum- Olefin complex; platinum(0)-divinyltetramethyldisiloxane complex; Examples of catalysts other than platinum _compounds include RhCl( _PPh3 ) ₃ , _RhCl3 , _RuCl3 , _IrCl3 , _FeCl3 , _AlCl3 , _PdCl2.H2O , _NiCl2 , _TiCl4 .

[2. naphthoquinonediazide compound (II)]
In one embodiment of the present invention, naphthoquinonediazide compound (II) is used as a photoacid generator. Conventionally, photoacid generators blended in curable compositions have generally been substances that generate strong acids such as sulfonic acid (see, for example, Examples in Patent Document 2). However, according to one embodiment of the present invention, the acid generated when the naphthoquinonediazide compound (II) is irradiated with light is a relatively weak carboxylic acid (indenecarboxylic acid). Although it is an acid generator that generates such a weak acid, the addition of the naphthoquinonediazide compound (II) improves the curability and curing rate of the curable composition. The result was unexpected.

Indenecarboxylic acid produced by photodecomposition of the naphthoquinonediazide compound (II) has good compatibility with the (meth)acrylate polymer (I). Therefore, the indene carboxylic acid is believed to function as a low molecular weight plasticizer. From this, it is expected that the addition of the naphthoquinonediazide compound (II) is effective in improving adhesion due to the carboxy group.

Examples of naphthoquinone diazide compounds (II) include ortho-naphthoquinone diazide, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2-naphthoquinone diazide 5-sulfonic acid ester, 1,2-naphthoquinone-2- diazido-6-sulfonic acid, 1,2-naphthoquinone-2-diazide-7-sulfonic acid, 1,2-naphthoquinone-2-diazide-5,6-disulfonic acid, 1,2-naphthoquinone-2-diazide-5 ,7-disulfonic acid, sodium, potassium, magnesium of 1,2-naphthoquinone-2-diazide-5,8-disulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid aryl ester compound, 1,2- diazido-2-sulfochloride/acetone/pyrogallol condensate.

Among the above naphthoquinone diazide compounds (II), ortho-naphthoquinone azide and 1,2-naphthoquinone diazide-sulfonic acid ester are preferred, and 1,2-naphthoquinone-2-diazide-4-sulfonic acid and 1,2-naphthoquinone diazide are preferred. 5-sulfonic acid esters are more preferred.

In the curable composition according to one embodiment of the present invention, the amount of the naphthoquinonediazide compound (II) is not particularly limited. The lower limit of the amount of the naphthoquinone diazide compound (II) is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more when the amount of the (meth)acrylic acid ester polymer (I) is 100 parts by weight. is more preferred, and 2 parts by weight or more is even more preferred. The upper limit of the amount of the naphthoquinonediazide compound (II) is preferably 10 parts by weight or less, more preferably 8 parts by weight or less, based on 100 parts by weight of the (meth)acrylic acid ester polymer (I). 7.5 parts by weight or less is more preferable. When the amount of the naphthoquinonediazide compound (II) is within the above range, the curable composition can be provided with good curability and curing speed.

[3. Water (III)]
A curable composition according to one embodiment of the present invention may comprise water (III). The curing speed can be increased by including water in the curable composition. The type of water (III) is not particularly limited. Examples of (III) include tap water, pure water, ion-exchanged water, distilled water, and ultrapure water. The amount of water (III) added in the curable composition is not particularly limited. From the viewpoint of increasing the curing speed, it is preferably 0.001 to 1% by weight based on the total weight of the curable composition. Also, considering the balance between the dispersibility of the curable composition and the curing speed, it is preferably 0.005% by weight to 0.5% by weight.

[4. Epoxy resin (IV)]
An epoxy resin (IV) may be added to the curable composition according to one embodiment of the present invention for the purpose of improving the strength and adhesiveness of the cured product. Epoxy resin (IV) is not particularly limited as long as it is a compound containing one or more epoxy groups in the molecule. Specific examples of the epoxy resin (IV) include bisphenol polyglycidyl ether type epoxy resins (bisphenol A type epoxy resin, bisphenol B type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, etc.); hydrogenated bisphenol type diglycidyl ether obtained by hydrogenating bisphenol polyglycidyl ether type epoxy resin (hydrogenated bisphenol A type epoxy resin, etc.); glycidyl ester type epoxy Resin; Glycidylamine type epoxy resin; Glycidyl ether of aliphatic polyhydric alcohol (ethylene glycol diglycidyl ether, 1,3-propylene glycol diglycidyl ether, 1,2-propylene glycol diglycidyl ether, 1,4-butanediol diol glycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri(glycidyloxymethyl)propane, 1,1,1-tri(glycidyloxymethyl)ethane, 1,1,1-tri(glycidyloxymethyl)methane, 1,1,1,1-tetra(glycidyloxymethyl)methane, glycerin triglycidyl ether, tri methylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, etc.); Polyglycidyl ethers of ether polyols; novolak type epoxy compounds (phenol novolak type epoxy resins, alkyl novolak type epoxy resins, biphenyl novolak type epoxy compounds, cresol novolak type epoxy compounds, bisphenol A novolac type epoxy compounds, dicyclo pentadiene novolac-type epoxy compound, etc.); Epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4- Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, bis(3,4-epoxycyclohexylmethyl)adipate, methylenebis(3,4-epoxycyclohexane), isopropylidenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexanecarboxylate), 1,2-epoxy-2-epoxyethylcyclohexane, etc.); aromatic epoxy resins (naphthalene type epoxy resin, biphenyl-type epoxy resin, anthracene-type epoxy resin, etc.); dibasic acid glycidyl ester (diglycidyl phthalate, tetrahydrophthalate diglycidyl ester, dimer acid glycidyl ester, etc.); flame-retardant epoxy resin (fluorinated epoxy resin, brominated epoxy resin, rubber-modified epoxy resin containing polybutadiene or NBR, glycidyl ether of tetrabromobisphenol A, etc.); p-oxybenzoic acid glycidyl ether ester type epoxy resin; m-aminophenol type epoxy resin; diaminodiphenylmethane epoxy resin; urethane-modified epoxy resin having a urethane bond; N,N-diglycidylaniline; N,N-diglycidyl-o-toluidine; hydantoin-type epoxy resin; be done. Epoxy resin (IV) may be used alone or in combination of two or more.

A commercially available product may be used as the epoxy resin (IV). Commercially available examples include UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200, UVR-6228, ERL-4299, ERL-4221 (manufactured by Union Carbide); Celoxide 2021 , Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 2000, Celoxide 3000, Cychroma-A200, Cychroma-M100, Cychroma-M101, Epoly-D GT-301, Epoly-D GT-302, Epoly-D GT- 401, Epolyde GT-403, EHPE3150, Epolyde HD300ETHB, Epoblend (manufactured by Daicel Chemical Industries, Ltd.); -4030, ADEKA RESIN EPR-4033, ADEKA RESIN EP-4080, ADEKA RESIN EP-4085, ADEKA RESIN EP-4088, ADEKA RESIN EP-4100, ADEKA RESIN EP-4100G, ADEKA RESIN EP-4100E, ADEKA RESIN EP-4100TX, ADEKA RESIN EP-4300E, ADEKA RESIN EP -4340, ADEKA RESIN EP-4400, ADEKA RESIN EP-4500A, ADEKA RESIN EP-4520S, ADEKA RESIN EP-4520TX, ADEKA RESIN EP-4530, ADEKA RESIN EP-4900, ADEKA RESIN EP-4901, ADEKA RESIN EP-4901F, ADEKA RESIN EP-4950, ADEKA RESIN EP -5100-75X, ADEKA RESIN ED-505, ADEKA RESIN ED-506, ADEKA RESIN EPU-78-13S, ADEKA RESIN EP-49-23, ADEKA RESIN EP-49-25, ADEKA RESIN KRM-2110, ADEKA RESIN KRM-2199, ADEKA RESIN KRM-2720 , ADEKA GLYCIROL ED-509S, ADEKA GLYCIROL ED-518S, ADEKA GLYCIROL ED-501, ADEKA GLYCIROL ED-502S, ADEKA GLYCIROL ED-509E, ADEKA GLYCIROL ED-529, ADEKA GLYCIROL ED-518, ADEKA GLYCIROL ED-503, ADEKA GLYCIROL ED-506, ADEKA GLYCIROL ED-523T, ADEKA GLYCIROL ED-515, ADEKA GLYCIROL ED-505, ADEKA GLYCIROL ED-5 ０５Ｒ（以上、旭電化工業社製）；ｊＥＲ１９０Ｐ、ｊＥＲ１９１Ｐ、ｊＥＲＹＸ３１０、ｊＥＲＤＸ２５５、ｊＥＲ５１７、ｊＥＲ５４５、ｊＥＲＹＸ８０００、ｊＥＲＹＸ８０３４、ｊＥＲＹＸ４０００、ｊＥＲＹＬ６１２１Ｈ、ｊＥＲＹＬ６６４０、ｊＥＲＹＬ６６７７、ｊＥＲ６０４、ｊＥＲ８０１、ｊＥＲ８２５、ｊＥＲ８２７、ｊＥＲ８２８、ｊＥＲ８３４、ｊＥＲ８０１、ｊＥＲ８０１Ｐ 、ｊＥＲ８０２、ｊＥＲ８１５、ｊＥＲ８１６Ａ、ｊＥＲ８１９、ｊＥＲ１００１、ｊＥＲ１００２、ｊＥＲ１００３、ｊＥＲ１０５５、ｊＥＲ１００４、ｊＥＲ１００７、ｊＥＲ１００９、ｊＥＲ１０１０、ｊＥＲ１００３Ｆ、ｊＥＲ１００４Ｆ、ｊＥＲ１００５Ｆ、ｊＥＲ８０６、ｊＥＲ８０６Ｌ、ｊＥＲ８０７、ｊＥＲ４００４Ｐ、ｊＥＲ４００７Ｐ、ｊＥＲ４０１０Ｐ、ｊＥＲ４１１０、ｊＥＲ４２１０、ｊＥＲ１２５６、ｊＥＲ４２５０ 、ｊＥＲ４２７５、ｊＥＲ１２５５ＨＸ３０、ｊＥＲ５５８０ＢＰＸ４０、ｊＥＲＹＸ８１００ＢＨ３０、ｊＥＲ１５２、ｊＥＲ１５４、ｊＥＲ１５７Ｓ７０、ｊＥＲ１８０Ｓ７０、ｊＥＲ１０３１Ｓ、ｊＥＲ１０３２Ｈ６０、ｊＥＲ６０４、ｊＥＲ６３０、ｊＥＲ８７１、ｊＥＲ８７２、ｊＥＲ８７２Ｘ７５、ｊＥＲ１０３１、ｊＥＲＲＸＥ１５、ｊＥＲＹＤＥ－２０５、ｊＥＲＹＤＥ－３０５、ｊＥＲＢＧＥ、ｊＥＲＹＥＤ１１１、ｊＥＲＹＥＤ１１１Ａ、ｊＥＲＹＥＤ１１１Ｅ , jERYED122, jERYED205, jERYED216 (manufactured by Japan Epoxy Resin Co., Ltd.); PY-306, 0163, DY-022 (manufactured by Ciba Geigy Co., Ltd.); Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF, Epolite 4000, Epolite 3002, Epolite FR-1500 (manufactured by Kyoeisha Chemical Co., Ltd.); R-508, R-531, R-710 (manufactured by Mitsui Chemicals); Sumepoxy ELM-120, Sumepoxy ELM-434 (manufactured by Sumitomo Chemical); Denacol EX-111, Denacol EX-121, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-147, Denacol EX-171, Denacol EX-192, Denacol EM-150, Denacol EX-201, Denacol EX-211, Denacol EX-212, Denacol EX-252, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-322, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-711, Denacol EX-721, Denacol EX-731, Denacol EX-810, Denacol EX-811, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-850, Denacol EX-851, Denacol EX-861, Denacol EX-911, Denacol EX941, Denacol EX-920, Denacol EX-931 (manufactured by Nagase ChemteX Corporation); Epiol B, Epiol EH, Epiol L-41, Epiol SK, Epiol A, Epiol P, Epiol SB, Epiol TB, Epiol BE-200, Epiol OH, Epiol G-100, Epiol E-100, Epiol E-400, Epiol E-1000, Epiol NPG-100, Epiol TMP-100, Marproof G- 0115S, Marproof G-0130S-P, Marproof G-0150M, Marproof G-0250S, Marproof G-1005S, Marproof G-1005SA, Marproof G-1010S, Marproof G-2050M, Marproof G- 01100, Marproof G-017581, Nusizer 510R, Nusizer 512 (manufactured by NOF Corporation); PY-306, 0163, DY-022 (manufactured by Ciba Specialty Chemicals); Epototo YD-012, Epototo YD-013, Epototo YD-014, Epototo YD-017, Epototo YD-019, Epototo YD-020G, Epototo YD-115, Epototo YD-118T, Epototo YD-127, Epototo YD-128, Epototo YD-134, Epototo YD-171, Epototo YD-172, Epototo YD-175X75, Epototo YD- 6020, Epototo YD-716, Epototo YD-7011R, Epototo YD-901, Epototo YD-902, Epototo YD-903N, Epototo YD-904, Epototo YD-907, Epototo YD-6020, Epototo YDF-170, Epototo YDF- 2001, Epototo YDF-2004, Epototo YDF-2005RL, Epototo YD-8125, Epototo YDF-8170C, Epototo ZX-1059, Epototo YD-825GS, Epototo YD-870GS, Epototo PG-207GS, Epototo ZX-1658GS, Epototo ZX- 1542, Epototo YDPN-638, Epototo YDCN-700-2, Epototo YDCN-700-3, Epototo YDCN-700-5, Epototo YDCN-700-7, Epototo YDCN-700-10, Epototo YDCN-704, Epototo YH- 300, Epototo YH-300, Epototo YH-301, Epototo YH-315, Epototo YH-324, Epototo YH-325, Neototo PG-202, Neototo PG-207N, Neototo PP-101, Neototo S, Epototo ST-3000, Epototo ST-4000D (manufactured by Toto Kasei Co., Ltd.); BREN-S, EPPN-201, EPPN-501N, EOCN-1020, GAN, GOT (manufactured by Nippon Kayaku Co., Ltd.); SB-20 (manufactured by Okamura Oil Co., Ltd.) ); Epiclon 720 (manufactured by Dainippon Ink and Chemicals Co., Ltd.); Epoxy resin (IV) may be used alone or in combination of two or more.

The epoxy resin (IV) preferably has two or more epoxy groups in one molecule. A curable composition containing such an epoxy resin (IV) has high reactivity in a curing reaction, and the cured product tends to form a three-dimensional network structure. Alicyclic epoxy resins are also preferred as the epoxy resin (IV). A curable composition containing an alicyclic epoxy resin has a transparent cured product and excellent curability.

Considering the above conditions, the epoxy resin (IV) is more preferably 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5 -methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl -3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, and bis(3,4-epoxycyclohexylmethyl)adipate.

In the curable composition according to one embodiment of the present invention, the amount of the epoxy resin (IV) to be blended is not particularly limited, and can be appropriately set according to the application and purpose. The lower limit of the amount of the epoxy resin (IV) is preferably 1 part by weight or more, more preferably 5 parts by weight or more, and more preferably 10 parts by weight when the amount of the (meth)acrylic acid ester polymer (I) is 100 parts by weight. Part by weight or more is more preferable. The upper limit of the amount of the epoxy resin (IV) is preferably 10,000 parts by weight or less, preferably 2,000 parts by weight or less, when the amount of the (meth)acrylic acid ester polymer (I) is 100 parts by weight. More preferably, 1,000 parts by weight or less is even more preferable. If the amount of the epoxy resin (IV) is too large, the cured product tends to be hard and the peel strength tends to decrease. If the amount of the epoxy resin (IV) is too small, the adhesive strength and water-resistant adhesiveness to the substrate tend to decrease.

[4.1. Epoxy resin curing agent]
The curable composition according to one embodiment of the present invention may use an epoxy resin curing agent in combination with the epoxy resin (IV).

As the epoxy resin curing agent, conventionally known ones can be widely used. Examples of epoxy resin curing agents include aliphatic amines (ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, methylpentamethylenediamine, trimethylhexamethylenediamine, guanidine, tetramethylguanidine , oleylamine, etc.); alicyclic amines (mensendiamine, isophoronediamine, norbornanediamine, piperidine, N,N'-dimethylpiperazine, N-aminoethylpiperazine, BASF Ramilon C-260, CIBA Araldit HY -964, Rohm and Haas Mensendiamine, 1,2-diaminocyclohexane, diaminodicyclohexylmethane, bis(4-amino-3-methylcyclohexyl)methane, bis(4-aminocyclohexyl)methane, polycyclohexylpolyamine, 1 ,8-diazabicyclo[5,4,0]undecene-7 (DBU), etc.); aromatic amines (m-xylylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diamino diphenyl sulfone, etc.); linear diamine represented by (CH ₃ ) ₂ N(CH ₂ ) _n N(CH ₃ ) ₂ (wherein n is an integer of 1 to 10); (CH ₃ ) ₂ —N(CH ₂ ) A linear tertiary amine represented by n _- CH ₃ ( _wherein n is _{an integer} of 0 to 10) _; alkyl tertiary monoamines shown; fatty aromatic amines such as benzyldimethylamine, 2-(dimethylaminomethyl)phenol, or 2,4,6-tris(dimethylaminomethyl)phenol; ether linkage-containing amines ( 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane (ATU), morpholine, N-methylmorpholine, polyoxypropylenediamine, polyoxypropylenetriamine, polyoxyethylenediamine, etc.); hydroxyl group-containing amines (diethanolamine, triethanolamine, etc.); triethylenediamine; pyridine; picoline; diazabicycloundecene; , benzophenonetetracarboxylic anhydride, tetrahydrophthalic anhydride, methyltetrahydroanhydride phthalic acid, methylnadic anhydride, hexahydrophthalic anhydride, dodecyl succinic anhydride, etc.); polyamidoamines (polyamides obtained by reacting dimer acid or other polycarboxylic acids with polyamines (diethylenetriamine, triethylenetetramine, etc.) and polyamide resin, etc.); imidazoles (2-ethyl-4-methylimidazole, etc.); dicyandiamide and its derivatives; polyoxypropylene-based amines (polyoxypropylene-based diamine, polyoxypropylene-based triamine, etc.); (epoxy-modified amines obtained by reacting the above-mentioned amines with epoxy compounds, Mannich-modified amines obtained by reacting the above-mentioned amines with formalin or phenols, Michael addition-modified amines, condensation of amine compounds and carbonyl compounds ketimine obtained by reaction); amine salts (2,4,6-tris(dimethylaminomethyl)phenol 2-ethylhexanoate, etc.); Examples include ketimine compounds.

A commercially available product may be used as the epoxy resin curing agent. Examples of commercially available products include Ankamin AD, Ankamin T-1, Ankamin 1644, Ankamin 1769, Ankamin 1833, Ankamin 1856, Ankamin 2089M, Ankamin 2089J, Ankamin 2390, Ankamin 2410, Ankamin 2422, Ankamin 2432, Ankamin 2606, Ankamin 2049. , ancamine 2167, ankamine 2264, ankamine MCA, ankamine 1618, ankamine 1732, ankamine 1884, ankamine 1943, ankamine 2074, ankamine 2143, ankamine 2199, ankamine 2280, ankamine 2558, ankamine 2559, ankamine 2596, ankamine 2631, ankamine 2632 2228, Ancamine 2489, Ancamine 2558, Ancamine 2597, Ancamine 2620, Ancamine Hardener PH-815, Hardener PH-816, Hardener PH-821, Hardener PH-826, Hardener PH-875, Hardener PH-895, Eye Japan Co., Ltd.); EH-451B, EH-451BA, EH-451K, EH-455, EH-253-9, EH-253-9A, EH-227B, EH-406A-2, EH-464EH-262W-4C, EH-4198- 1, EH-4199-4, EH-4199-4B, EH-461, EH-273, EH-233W, EH-233B, EH-3895, EH-404 (manufactured by ADEKA), Epomate B001, Epomate B002 , EPOMATE B002W, EPOMATE B002R, EPOMATE C002, EPOMATE N001, EPOMATE N002, EPOMATE P002, EPOMATE RX2, EPOMATE RX221, EPOMATE RX3, EPOMATE RX32, EPOMATE QX2, EPOMATE QX3, EPOMATE LX1N, EPOMATE SWRDX1 EPOMATE, EPOMATE LX1S LX2S, Epomate LX2W, Epomate SA1 (manufactured by Japan Epoxy Resin Co., Ltd.); Tomide 210, Tomide 215X, Tomide 225E, Tomide 225X, Tomide 225R, Tomide 225ND, Toma Ido 235A, Tomide 235R, Tomide 235S, Tomide 241, Tomide 245, Tomide 245S, Tomide 245HS, Tomide 245LP, Tomide 252A, Tomide 255A, Tomide 275FA, Tomide 280C, Tomide 290CA, Tomide 290FA, Tomide 292A, Tomide 211, Tomide 296 , Tomide 2400, Tomide 2500, Tomide 2510, Tomide 2602, Tomide RS640, Tomide HR11, Tomide TXE524, Tomide 410N, Tomide 215-70X, Tomide 423, Tomide 437, Tomide TXC636A, Tomide TXS53C, Tomide TXC636A, Tomide TXS53C, Tomide TXH675B0, 0 Fuji 、フジキュアー５００３、フジキュアー５１００、フジキュアー５２６０Ｆ、フジキュアー５３００、フジキュアー５４００、フジキュアー５４０５、フジキュアー５４１０、フジキュアー５４２０Ａ、フジキュアー５４２０Ｆ、フジキュアーＺＳ４、フジキュアー４２３３Ｆ、フジキュアー６３００、フジキュアーＦＸＵ８２２、フジキュアーＦＸＵ８４８、フジキュアーＦＸＵ８７０、フジキュアー４０１１、フジキュアー4025, Fujicure 4030, Fujicure FXI919, Fujicure FXH927, Fujicure FXR1020, Fujicure 1030, and Fujicure 1081 (manufactured by Fuji Kasei).

Epoxy resin curing agents may be used alone or in combination of two or more. Among the epoxy resin curing agents described above, aliphatic amine curing agents are preferable from the viewpoint of excellent transparency and non-coloring properties of the cured product. Further, modified aliphatic amines are more preferable from the viewpoint of excellent curability of the curable composition and good compatibility with the (meth)acrylic acid ester-based polymer (I). Examples of such modified aliphatic amines include Fujicure FXU870 and Fujicure 5420F.

The blending amount of the epoxy resin curing agent can be determined based on the active hydrogen equivalent. However, in consideration of the decrease in the viscosity of the curable composition and the reactivity at low temperatures, it may be blended in an excess amount relative to the equivalent amount, or may be blended in an amount insufficient relative to the equivalent amount. The lower limit of the amount of the epoxy resin curing agent is preferably 0.5 parts by weight or more, more preferably 1.0 parts by weight or more, based on 100 parts by weight of the total weight of the polymer having a crosslinkable silyl group. The upper limit of the amount of the epoxy resin curing agent is preferably 60 parts by weight or less, more preferably 50 parts by weight or less, based on 100 parts by weight of the total weight of the polymer having a crosslinkable silyl group. Here, the total weight of the crosslinkable silyl group-containing polymer includes the (meth)acrylate polymer (I) and the optional polyether polymer (VI). If the amount is less than 0.5 parts by weight, curing of the epoxy resin becomes insufficient, and the strength of the cured product tends to decrease. If the blending amount exceeds 60 parts by weight, bleeding may occur and the appearance of the cured product may be impaired.

[5. Silane coupling agent (V)]
A curable composition according to one embodiment of the present invention may contain a silane coupling agent (V).

The silane coupling agent (V) is not particularly limited, and conventionally known agents can be widely used. Examples of the silane coupling agent (V) include silane coupling agents having functional groups (amino group, mercapto group, epoxy group, carboxyl group, vinyl group, isocyanate group, isocyanurate, halogen, etc.). More specific examples of the silane coupling agent (V) include isocyanate group-containing silanes (γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanate propylmethyldimethoxysilane, etc.); amino group-containing silanes (γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyl methyldiethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-( 2-aminoethyl)aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl -γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, etc.); Mercapto group-containing silanes (γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyl methyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, etc.); epoxy group-containing silanes (γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane , β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, etc.); carboxysilanes (β-carboxyethyltriethoxysilane, β-carboxyethylphenyl bis(2-methoxyethoxy)silane, N-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane, etc.); vinyl type unsaturated group-containing silanes (vinyltrimethoxysilane, vinyltriethoxysilane, γ -methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyltriethoxysilane, etc.); halogen-containing silanes (γ-chloropropyltrimethoxysilane, etc.); Anurate silanes (tris(trimethoxysilyl)isocyanurate, etc.); polysulfans (bis(3-triethoxysilylpropyl)tetrasulfane, etc.). Examples of further silane coupling agents (V) include reaction products of amino group-containing silanes and epoxy group-containing silanes; reaction products of amino group-containing silanes and acryloyloxy group-containing silanes; Reaction products of silanes and isocyanate group-containing silanes; derivatives obtained by modifying the above silane coupling agents (amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, blocked isocyanate silanes, silylated polyesters, etc.); and ketimine compounds obtained by reacting amino group-containing silanes with ketone compounds (methyl isobutyl ketone, etc.). Silane coupling agents (V) may be used alone or in combination of two or more.

Among the silane coupling agents (V) described above, aminosilane and epoxysilane are preferable from the viewpoint of excellent strength of the cured product and excellent adhesiveness to adherends (such as mortar). Furthermore, considering the transparency of the cured product, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, and γ-(2-aminoethyl)aminopropyl More preferably, one or more selected from the group consisting of methyldimethoxysilane.

Epoxysilane and vinylsilane are preferred from the viewpoint of excellent storage stability of the curable composition. Considering also the transparency of the cured product, one or more selected from the group consisting of γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and vinyltrimethoxysilane are more preferable.

The lower limit of the amount of the silane coupling agent (V) is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, based on 100 parts by weight of the (meth)acrylate polymer (I). . The upper limit of the amount of the silane coupling agent (V) is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the (meth)acrylate polymer (I). If the amount is too small, the adhesiveness of the curable composition to the adherend and the strength of the cured product may decrease. If the amount is too large, the curability of the curable composition and the transparency of the cured product may be lowered.

[6. Polyether polymer (VI)]
The curable composition according to one embodiment of the present invention may contain a polyether polymer (VI) having an average of one or more crosslinkable silyl groups per molecule.

Examples of the polyether polymer (VI) include polyether polymers described in paragraphs [0139] to [0158] of JP-A-2007-308716 and paragraphs [0136] to [0149] of JP-A-2007-308692. Among ether-based polymers, those containing a crosslinkable silyl group can be mentioned.

The main chain structure of the polyether polymer (VI) is not particularly limited. The polyether polymer (VI) may or may not contain urethane bonds and/or urea bonds in its main chain. Examples of the main chain of the polyether polymer (VI) include polyethylene oxide, polypropylene oxide, polybutylene oxide and polyphenylene oxide.

The main chain of the polyether polymer (VI) preferably contains oxyalkylene units as a main component, and more preferably contains propylene oxide units as a main component. Here, in relation to the main chain of the polymer, the term "contains as a main component" means 50 mol% or more (preferably 70 mol% or more, more preferably 90% or more) of the monomer units constituting the main chain. is occupied by a specific monomer. Therefore, "the main chain of the polyether polymer (VI) is mainly composed of oxyalkylene units" means that the main chain of the polyether polymer (VI) is 50 mol% or more (preferably 70 mol % or more) is occupied by oxyalkylene units. The main chain of the polyether polymer (VI) may contain ethylene oxide units, butylene oxide units, phenylene oxide units, etc., in addition to propylene oxide units.

The polyether polymer (VI) is preferably a polypropylene oxide polymer having a molecular weight distribution (Mw/Mn) of 1.5 or less. Such a polyether polymer (VI) has a low viscosity and is easy to handle.

As the crosslinkable silyl groups contained in the polyether polymer (VI), the crosslinkable silyl groups described in relation to the (meth)acrylate polymer (I) can be employed.

Commercially available products can be used as the polyether polymer (VI). Examples of commercially available products include MS Polymer S203, MS Polymer S303, MS Polymer S810, MS Polymer S943, Silyl SAT200, Silyl SAT350, Silyl SAX220, Silyl SAT400, Silyl EST280, Silyl MA440, Silyl MA903 (manufactured by Kaneka Corporation). and Exester ES-S3620, ES-S3430, ES-S2420, ES-S2410 (manufactured by Asahi Glass Co., Ltd.). The polyether polymer (VI) may be used alone or in combination of two or more.

The lower limit of the amount of the polyether polymer (VI) is preferably 1 part by weight or more, more preferably 5 parts by weight or more, and more preferably 10 parts by weight when the (meth)acrylic acid ester polymer (I) is 100 parts by weight. Part by weight or more is more preferable. The upper limit of the amount of the polyether polymer (VI) is preferably 10,000 parts by weight or less, preferably 2,000 parts by weight or less, when the (meth)acrylic acid ester polymer (I) is 100 parts by weight. More preferably, 1,000 parts by weight or less is even more preferable. If the amount of the polyether polymer (VI) added is too large, the heat resistance and weather resistance of the cured product may deteriorate.

[7. Amine Compound (VII) and Amine Precursor Compound (VII-A)]
The curable composition according to one embodiment of the present invention may or may not contain the amine compound (VII) and/or the amine precursor compound (VII-A). Curable compositions that do not contain amine compound (VII) and/or amine precursor compound (VII-A) tend to have improved storage stability. This is because the naphthoquinonediazide compound (II) before irradiation with light is not an acid, and the curable composition can be made whole by blending the amine compound (VII) and/or the amine precursor compound (VII-A). This is because it becomes basic as

However, the effect of the amine compound (VII) and/or the amine precursor compound (VII-A) on storage stability varies depending on the type of compound. The compounds used in the examples below have relatively little effect on storage stability.

Preferred amine compounds (VII) are monoamines and polyamines. Examples of monoamines and polyamines include aliphatic amines, aromatic amines, heterocyclic amines. As the amine precursor compound (VII-A), a photobase (amine) generator and a thermal base (amine) generator are preferable, and a photobase (amine) generator is more preferable.

Examples of aliphatic amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, triethanolamine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-diisopropylamine. Ethylamine, tetramethylethylenediamine, hexamethylenediamine, spermidine, spermine, amantadine.

Examples of aromatic amines include aniline, phenethylamine, toluidine, catecholamines, 1,8-bis(dimethylamino)naphthalene.

Examples of heterocyclic amines include pyrrolidine, piperidine, piperazine, morpholine, quinuclidine, 1,4-diazabicyclo[2.2.2]octane, pyrrole, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, oxazole, thiazole. , 4-dimethylaminopyridine.

Examples of photolatent amine-generating compounds include coumaric acid amide derivatives, carbamate derivatives, reactants of organic carboxylic acids with imidazoles, reactants of organic carboxylic acids with cyclic amines, salts of organoboron compounds and biguanide compounds, Examples include salts of organic carboxylic acids and biguanide compounds. More specific examples include 9-anthorylmethyl N,N-ethyl carbonate, (E)-1-piperinido-3-(2-hydroxyphenyl)-2-propen-1-one, 1-(anthoraquinone-2 -yl) ethylimidazole-1-carbonate, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carbonate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate , (Z)-{[bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methamiminidium tetrakis(3-fluorophenyl)borate, 1,2-diisopropyl-3-[bis(dimethylamino) methylene]guanidinium-2-(3-benzoylphenyl)propionate.

Among the above, triethylamine, ethylenediamine, triethanolamine, in terms of compatibility with the resin component contained in the curable composition, non-volatility, and ease of forming a salt with the carboxylic acid component generated after light irradiation. , N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-diisopropylethylamine, aniline, phenethylamine, toluidine, piperidine, piperazine, 1,2-dicyclohexyl-4,4,5,5-tetra methylbiguanidinium n-butyltriphenylborate, 1,4-diazabicyclo[2.2.2]octane, tetrakis(3-fluorophenyl)borate, and 1,2-diisopropyl-3-[bis(dimethylamino)methylene ] One or more selected from the group consisting of guanidinium-2-(3-benzoylphenyl)propionate is preferred. Further considering curing activity, N,N-dimethylaminopropylamine, piperidine, piperazine, 1,4-diazabicyclo[2.2.2]octane, 1,2-dicyclohexyl-4,4,5,5-tetramethyl More preferably, one or more selected from biguanidinium n-butyltriphenylborate, 1,4-diazabicyclo[2.2.2]octane, and tetrakis(3-fluorophenyl)borate.

[8. Other ingredients]
A curable composition according to one embodiment of the present invention may contain components other than those described above. Examples of such components include adhesion-imparting agents, fillers, plasticizers, solvents, thixotropic agents, light-curing substances, oxygen-curing substances, antioxidants, ultraviolet absorbers, and other additives. mentioned. Each component will be described below.

[8.1. Adhesive agent]
The tackifier is not particularly limited. In one embodiment, the adhesion-imparting agent is the silane coupling agent (V) described above. Examples of adhesion promoters other than the silane coupling agent (V) include phenol resins, sulfur, alkyl titanates, and aromatic polyisocyanates. Adhesion imparting agents may be used alone or in combination of two or more.

[8.2. filler]
Examples of fillers include fillers or fine hollow particles described in paragraphs [0134] to [0151] of JP-A-2006-291073. More specific examples of fillers include reinforcing silica finely divided silica (fumed silica, wet silica, etc.), wood flour, pulp, cotton chips, asbestos, mica, walnut shell powder, rice husk powder, and graphite. , clay, silica (crystalline silica, fused silica, dolomite, silicic anhydride, hydrated silicic acid, etc.), carbon black, ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, oxidation Titanium, bentonite, organic bentonite, ferric oxide, red iron oxide, fine aluminum powder, flint powder, zinc oxide, active zinc white, zinc dust, zinc carbonate, shirasu balloon, fibrous filler (glass fiber, glass filament, carbon fiber , Kevlar fiber, polyethylene fiber, etc.). A filler may be used independently and may use two or more types together.

[8.3. Plasticizer]
By adding a plasticizer, the viscosity of the curable composition and the mechanical properties (tensile strength, elongation, etc.) of the cured product can be adjusted. Moreover, the transparency of the cured product can be improved by adding a plasticizer.

Examples of plasticizers include phthalates (dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, butylbenzyl phthalate, etc.); non-aromatic dibasic acid esters (dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, etc.); aliphatic esters (butyl oleate, methyl acetylricinoleate, etc.); Acid esters (tricresyl phosphate, tributyl phosphate, etc.); trimellitic acid esters; polystyrenes (polystyrene, poly-α-methylstyrene, etc.); polybutadiene; polybutene; polyisobutylene; butadiene-acrylonitrile; Paraffins; Hydrocarbon oils (alkyldiphenyl, partially hydrogenated terphenyl, etc.); Process oils; Polyethers (polyether polyols (polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.), hydroxyl groups of polyether polyols derivatives converted to ester groups or ether groups, etc.); epoxy plasticizers (epoxidized soybean oil, benzyl epoxy stearate, etc.); dibasic acids (sebacic acid, adipic acid, azelaic acid, phthalic acid, etc.); dihydric alcohols polyester plasticizers obtained from (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, etc.); vinyl polymers obtained by polymerizing vinyl monomers by various methods (acrylic plasticizers etc.). The plasticizer may be used alone or in combination of two or more.

[8.4. solvent]
Examples of solvents include aromatic hydrocarbon solvents (toluene, xylene, etc.); ester solvents (ethyl acetate, butyl acetate, amyl acetate, cellosolve acetate, etc.); ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketones, etc.); alcohol solvents (methanol, ethanol, isopropanol, etc.); hydrocarbon solvents (hexane, cyclohexane, methylcyclohexane, heptane, octane, etc.). A solvent may be used independently and may use two or more types together. The solvent may be used during production of the polymer, or may be used during mixing of each component.

[8.5. thixotropy-imparting agent]
Addition of a thixotropic agent to the curable composition prevents sagging and improves workability. The thixotropic agents may be used alone or in combination of two or more.

[8.6. Photocurable substance]
A photocurable substance is a substance whose molecular structure is changed in a very short time by the action of light and whose physical properties are changed (cured, etc.). When a photocurable substance is blended into the curable composition, a film of the photocurable substance is formed on the surface of the cured product, reducing stickiness of the cured product and improving weather resistance.

Examples of photocurable substances include unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, epoxy compounds, and vinyl ether compounds. Substances described in paragraphs [0256] to [0260] of WO05/095485 are also included. Specific examples of photocurable substances include special acrylates. Examples of special acrylates include bifunctional acrylates (Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245, etc.); 305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, etc.); ). The photocurable substance is preferably a compound containing an acrylic functional group, more preferably a compound containing three or more acrylic functional groups per molecule on average. A photocurable substance may be used independently and may use two or more types together.

[8.7. Oxygen Curable Substance]
When an oxygen-curable substance is added to the curable composition, it reacts with oxygen in the air to form a cured film near the surface of the cured product. Therefore, the stickiness of the surface of the cured product is reduced, and adhesion of dirt and dust is prevented.

Examples of oxygen-curable materials include unsaturated compounds that can react with oxygen in the air. More specific examples include drying oils (tung oil, linseed oil, etc.); alkyd resins obtained by modifying drying oils; polymers modified with drying oils (acrylic polymers, epoxy resins, silicone resins, urethane resin, etc.); 1,2-polybutadiene; 1,4-polybutadiene; C5-C8 diene polymer or copolymer; modified oil, etc.). In addition, substances described in paragraphs [0263] to [0264] of International Publication No. 05/095485 are also exemplified. The oxygen-curable substance is preferably used in combination with the photo-curable substance (see JP-A-03-160053). The oxygen-curable substances may be used alone, or two or more of them may be used in combination.

[8.8. Antioxidant]
Blending an antioxidant into the curable composition improves the heat resistance of the cured product. Examples of antioxidants include primary antioxidants (hindered phenol-based antioxidants, amine-based antioxidants, lactone-based antioxidants, etc.), secondary antioxidants (sulfur-based oxidants, phosphorus-based oxidants, etc.). Further examples of antioxidants include substances described in paragraphs [0232] to [0235] of JP-A-2007-308692 and paragraphs [0089] to [0093] of WO05/116134. . Antioxidants may be used alone or in combination of two or more.

[8.9. UV absorber]
Examples of UV absorbers include benzophenone UV absorbers, benzotriazole UV absorbers, salicylate UV absorbers, triazine UV absorbers, cyanoacrylate UV absorbers, substituted tolyl UV absorbers, and metal chelate UV absorbers. An ultraviolet absorber is mentioned. In one embodiment, the UV absorber included in the curable composition is a UV absorber that is not an oxalic acid anilide UV absorber and/or a malonic ester UV absorber. A triazine-based UV absorber is preferred because the cured product is less colored. Ultraviolet absorbers may be used alone or in combination of two or more.

[8.10. Other additives]
Other additives may be added in order to adjust various physical properties of the curable composition or cured product. Examples of other additives include curability modifiers, radical inhibitors, metal deactivators, antiozonants, phosphorus-based peroxide decomposers, lubricants, pigments, antifoaming agents, foaming agents, antitermites. agents and antifungal agents. Further examples of other additives include derivatives of oxypropylene polymers that produce R ₃ SiOH (such as trimethylsilanol) on hydrolysis (see JP-A-07-258534); A polymer having a silyl group to be a silanol-containing compound (see JP-A-06-279693); tetraalkoxysilane; silicate which is a partial hydrolysis condensate of tetraalkoxysilane; 108928, JP-A-63-254149, JP-A-64-22904, and JP-A-2001-72854. Other additives may be used alone or in combination of two or more.

[9. Preparation of curable composition]
The curable composition according to one embodiment of the present invention may be prepared as a one-component curable composition in which all the ingredients are pre-blended, sealed and stored, and cured by moisture in the air after use. . A one-pack type curable composition does not require the labor of mixing and kneading each component at the time of use, and there is no room for measuring errors of each component, so curing failure is less likely to occur.

The curable composition according to one embodiment of the present invention can also be prepared as a multi-component curable composition in which each component is separately blended into two or more liquids and mixed before use. The method of dividing each component may be appropriately determined in consideration of the mixing ratio of each component, storage stability, mixing method, pot life, and the like.

The curable composition can be prepared by mixing each component that constitutes the curable composition. Examples of the mixing method include mixing using a hand mixer or static mixer, mixing at room temperature or under heating using a roll or kneader, and mixing by dissolving the components in an appropriate solvent.

A cured product can be obtained by pouring the one-liquid type composition into a container, a mold, or the like and irradiating it with ultraviolet rays or the like. When a curable composition is used for laminating a plurality of adherends, the curable composition is applied to the first adherend, the second adherend is laminated, and then ultraviolet rays or the like are irradiated. can be hardened.

[10. Application]
Examples of applications of cured products obtained by curing the curable composition include pressure-sensitive adhesives, sealants (for buildings, ships, automobiles, roads, etc.), adhesives, molding agents, anti-vibration materials, Vibration damping materials, sound insulation materials, foam materials, paints, coating materials, spraying materials, electrical and electronic component materials, sealing materials, insulating materials, rust prevention/waterproof sealing materials, anti-vibration/vibration/sound/seismic isolation materials. Cured products are excellent in flexibility, adhesiveness and appearance, and are therefore suitable for paints, coating materials, sealants and adhesives.

[11. summary〕
The present invention includes the following aspects.
<1>
a (meth)acrylic ester-based polymer (I) having an average of one or more crosslinkable silyl groups per molecule;
a naphthoquinone azide compound (II);
A curable composition comprising:
<2>
The curable composition according to <1>, further comprising water (III).
<3>
The curable composition according to <1> or <2>, wherein the (meth)acrylate polymer (I) has a molecular weight distribution of less than 1.8.
<4>
The curable composition according to any one of <1> to <3>, wherein the crosslinkable silyl group is represented by the following general formula (1):
[Si(R ¹ ) _2-b (Y) _b O] _m -Si(R ² ) _3-a (Y) _a (1)
In formula (1),
R ¹ and R ² each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R′) ₃ SiO—. represents a triorganosiloxy group that is
when two or more of each of R ¹ or R ² are present, they may be the same or different;
R ' represents a monovalent hydrocarbon group having 1 to 20 carbon atoms,
Multiple R' may be the same or different,
Y represents a hydroxyl group or a hydrolyzable group,
when two or more Y are present, they may be the same or different;
a represents an integer of 0, 1, 2 or 3,
b represents an integer of 0, 1, or 2;
m represents an integer from 0 to 19,
satisfies a+mb≧1.
<5>
The curable composition according to any one of <1> to <4>, wherein the (meth)acrylic acid ester polymer (I) has a crosslinkable silyl group at the end of the molecular chain.
<6>
The curable composition according to any one of <1> to <5>, further comprising an epoxy resin (IV).
<7>
The curable composition according to any one of <1> to <6>, further comprising a silane coupling agent (V).
<8>
The curable composition according to any one of <1> to <7>, further comprising a polyether polymer (VI) having an average of one or more crosslinkable silyl groups per molecule.
<9>
The curable composition according to any one of <1> to <8>, further comprising an amine compound (VII).
<10>
The curable composition according to any one of <1> to <8>, further comprising an amine precursor compound (VII-A) that generates an amine compound upon irradiation with light.
<11>
A cured product obtained by curing the curable composition according to any one of <1> to <10>.

In addition to the above aspects, the present invention further includes the following aspects.
<A1>
The main chain of the (meth)acrylic acid ester polymer (I) may be produced by polymerizing mainly acrylic acid ester monomers.
<A2>
The main chain of the (meth)acrylate polymer (I) may be produced by living radical polymerization.
<A3>
The main chain of the (meth)acrylate polymer (I) may be produced by atom transfer radical polymerization.
<A4>
The epoxy resin (IV) may be an alicyclic epoxy resin.
<A5>
The silane coupling agent (V) may be at least one silane coupling agent selected from the group consisting of epoxysilane, aminosilane, and vinylsilane.
<A6>
The amine precursor compound (VII-A) includes a coumaric acid amide derivative, a carbamate derivative, a reaction product of an organic carboxylic acid and imidazole, a reaction product of an organic carboxylic acid and a cyclic amine, a salt of an organic boron compound and a biguanide compound, and at least one selected from the group consisting of salts of organic carboxylic acids and biguanide compounds.

Specific examples of the present invention are shown below, but the present invention is not limited to the following examples.

In the present Examples, the number average molecular weight and molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). As the stationary phase for GPC, a column packed with polystyrene crosslinked gel (shodex GPC K-804, K-802.5; manufactured by Showa Denko KK) was used. Chloroform was used as a mobile phase for GPC.

The number of functional groups introduced per polymer molecule was calculated based on concentration analysis by ¹ H-NMR and number average molecular weight. As an apparatus for NMR, ASX-400 (manufactured by Bruker) was used. Deuterated chloroform was used as a solvent for NMR. The NMR measurement temperature was 23°C.

[Synthesis Example 1]
A poly(n-butyl acrylate) polymer having a crosslinkable silyl group was synthesized as the (meth)acrylate polymer (I) by the following procedure.

(1) Polymerization step 1. 100 parts by weight of n-butyl acrylate was deoxygenated.
2. The inside of a stainless steel reaction vessel equipped with a stirrer was deoxidized, and 0.84 parts by weight of cuprous bromide and 20 parts by weight of the deoxidized n-butyl acrylate were charged and heated and stirred.
3.8.8 parts by weight of acetonitrile and 1.8 parts by weight of diethyl 2,5-dibromoadipate (initiator) were added and mixed.
4. When the temperature of the mixture was adjusted to about 80° C., 0.018 parts by weight of pentamethyldiethylenetriamine was added to initiate the polymerization reaction.
5. The remainder of n-butyl acrylate (80 parts by weight) was successively added to proceed with the polymerization reaction. During the polymerization, pentamethyldiethylenetriamine was appropriately added to adjust the polymerization rate. The total amount of pentamethyldiethylenetriamine used in the polymerization was 0.15 parts by weight. Since the internal temperature rises due to the heat of polymerization, the polymerization was allowed to proceed while adjusting the internal temperature to about 80 to about 90°C.
6. When the monomer conversion rate (polymerization reaction rate) reached about 95% or more, the volatile matter was removed under reduced pressure to obtain a polymer concentrate.

(2) Diene reaction step7. 21 parts by weight of 1,7-octa-1,7-octadiene, 35 parts by weight of acetonitrile and 0.34 parts by weight of pentamethyldiethylenetriamine were added to the polymer concentrate obtained in the polymerization step.
8. The mixture was heated and stirred for several hours while adjusting the internal temperature to about 80 to about 90°C. In this manner, the terminal of the polymer was reacted with octa-1,7-octadiene.

(3) Oxygen treatment step9. When the diene reaction step was completed, an oxygen-nitrogen mixed gas was introduced into the gas phase portion of the reaction vessel.
10. While controlling the internal temperature to be about 80 to about 90° C., the reaction solution was heated and stirred for several hours to bring oxygen into contact with the polymerization catalyst in the reaction solution.
11. Acetonitrile and unreacted 1,7-octadiene were removed by vacuum devolatilization to obtain a polymer-containing concentrate. The concentrate was highly colored.

(4) First crude purification step 12. The concentrate obtained in the oxygenation step was diluted with about 100-150 parts by weight of butyl acetate relative to the polymer.
13. After adding a filter aid and stirring, an insoluble catalyst component was filtered off. The resulting filtrate was colored and cloudy due to polymerization catalyst residues.

(5) Second crude purification step 14. The filtrate was charged into a stainless steel reactor equipped with a stirrer. As adsorbents, aluminum silicate (Kyoward 700SEN, manufactured by Kyowa Kagaku) and hydrotalcite (Kyoward 500SH, manufactured by Kyowa Kagaku) were added.
15. An oxygen-nitrogen mixed gas was introduced into the gas phase in the reaction vessel, and the mixture was heated and stirred at about 100° C. for 1 hour.
16. Insoluble components such as adsorbents were filtered off. The resulting filtrate was concentrated to obtain a crude polymer product.

(6) dehalogenation step (high-temperature heat treatment step) and adsorption purification step17. A thermal stabilizer (Sumilizer GS: manufactured by Sumitomo Chemical Co., Ltd.) and an adsorbent (Kyoward 700SEN, Kyoward 500SH) were added to the crudely purified polymer obtained in the second crude purification step.
18. The temperature was raised while devolatilizing under reduced pressure and heating with stirring. Vacuum devolatilization and heating and stirring were carried out at a high temperature of about 170 to about 200° C. for several hours to eliminate the halogen groups in the polymer and to purify the polymer by adsorption.
19. Additional adsorbents (Kyoward 700SEN and Kyoward 500SH) and diluent solvent (about 10 parts by weight of butyl acetate relative to the polymer) were added.
20. The gas phase portion in the reaction vessel was changed to an oxygen-nitrogen mixed gas atmosphere, and the mixture was heated and stirred at a high temperature of about 170 to about 200° C. for several hours to continue adsorption purification.
21. After the adsorption treatment, the polymer was diluted with 90 parts by weight of butyl acetate and filtered with an adsorbent. The filtrate was concentrated to obtain a polymer having alkenyl groups at both ends.

(7) Silylation step 22. 1.7 parts by weight of methyldimethoxysilane, 0.9 parts by weight of methyl orthoformate, and 0.0010 parts by weight of a platinum catalyst (bis(1,3-divinyl-1 , 1,3,3-tetramethyldisiloxane (isopropanol solution of platinum complex catalyst) was added, and the mixture was heated and stirred at about 100° C. for about 1 hour.
23. Volatile matter (such as unreacted methyldimethoxysilane) was distilled off under reduced pressure to obtain a polymer [P1] having dimethoxysilyl groups at both ends.

Polymer [P1] had a number average molecular weight of about 25,000 and a molecular weight distribution of 1.3. Polymer [P1] had an average of about 1.9 crosslinkable silyl groups per molecule.

[Synthesis Example 2]
A poly(n-butyl acrylate/ethyl acrylate/octadecyl acrylate) polymer having a crosslinkable silyl group was synthesized as the (meth)acrylate polymer (I) by the following procedure.

(1) Polymerization step 1. 100 parts by weight of acrylic ester monomer mixture A was prepared by mixing n-butyl acrylate:ethyl acrylate:octadecyl acrylate in a weight ratio of 71:11:18.
2. The interior of a stainless steel reaction vessel equipped with a stirrer was deoxidized, and 0.74 parts by weight of cuprous bromide and 20 parts by weight of acrylic acid ester monomer mixture A were charged and heated with stirring.
3.8.87 parts by weight of acetonitrile and 1.08 parts by weight of diethyl 2,5-dibromoadipate (initiator) were added and mixed.
4. After adjusting the temperature of the mixture to about 65° C., 0.015 parts by weight of pentamethyldiethylenetriamine was added to initiate the polymerization reaction.
5. The remainder (80 parts by weight) of the acrylic acid ester monomer mixture A was added successively to allow the polymerization reaction to proceed. During the polymerization reaction, pentamethyldiethylenetriamine was appropriately added to adjust the polymerization rate. The total amount of pentamethyldiethylenetriamine used throughout the polymerization reaction was 0.15 parts by weight. Since the internal temperature rises due to the heat of polymerization, the polymerization was allowed to proceed while adjusting the internal temperature to about 80 to about 90°C.
6. When the monomer conversion rate (polymerization reaction rate) reached about 95% or more, the volatile matter was removed under reduced pressure to obtain a polymer concentrate. The time required up to this stage was 5 hours.

(2) Diene reaction step7. 18.98 parts by weight of 1,7-octadiene, 135.49 parts by weight of acetonitrile, and 0.30 parts by weight of pentamethyldiethylenetriamine were added to the polymer concentrate obtained in the polymerization step.
8. The temperature of the reaction system was adjusted to about 80 to about 90° C. and the mixture was heated and stirred for 4 hours to allow 1,7-octadiene to react with the terminal of the polymer.

(3) First crude purification step9. When the diene reaction step was completed, an oxygen-nitrogen mixed gas was introduced into the gas phase portion of the reaction vessel.
10. While maintaining the temperature of the reaction system at about 80 to about 90° C., the reaction solution was heated and stirred for 4 hours to bring the polymerization catalyst contained in the reaction solution into contact with oxygen.
11. Acetonitrile and unreacted 1,7-octadiene were removed by devolatilization under reduced pressure to obtain a polymer concentrate. The time required for the steps up to this point was 6 hours.

(4) Second crude purification step 12. After diluting the polymer concentrate with 100 parts by weight of butyl acetate, a filter aid was added and stirred. After that, the insoluble catalyst component was filtered off.
13. The filtrate was placed in a stainless steel reactor equipped with a stirrer, and adsorbents (Kyoward 700SEN-S and Kyoward 500SH) were added.
14. An oxygen-nitrogen mixed gas was introduced into the gas phase in the reaction vessel, and the mixture was heated and stirred at about 100° C. for 1 hour. Thereafter, insoluble components (adsorbent, etc.) were filtered off to obtain a clear filtrate.
15. After repeating the above operation twice, the filtrate was concentrated to obtain a crude polymer product.

(5) dehalogenation step (high-temperature heat treatment step) and adsorption purification step16. A heat stabilizer (Sumilizer GS: manufactured by Sumitomo Chemical Co., Ltd.) and adsorbents (Kyoward 700SEN-S, Kyoward 500SH) were added to the crudely purified polymer.
17. The crude polymer product was purified by adsorption by heat stirring and vacuum devolatilization at a high temperature of about 170 to about 200° C. for about 2 hours.
18. The polymer was diluted by adding 10 times the amount of butyl acetate, and adsorbents (Kyoward 700SEN and Kyoward 500SH) were added.
19. The gas phase portion in the reaction vessel was changed to an oxygen-nitrogen mixed gas atmosphere, and the mixture was heated and stirred at a high temperature of about 170 to about 200° C. for about 4 hours to continue adsorption purification.
20. After diluting the polymer with 90 times the amount of butyl acetate, the adsorbent was filtered off. The filtrate was concentrated to obtain a polymer having alkenyl groups at both ends.

(6) Silylation step 21. Per 100 parts by weight of a polymer having alkenyl groups at both ends, 1.91 parts by weight of methyldimethoxysilane, 0.54 parts by weight of methyl orthoformate, 0.388 mL of bis(1,3-divinyl-1,1 ,3,3-tetramethyldisiloxane) platinum complex catalyst in isopropanol solution (1.32×10 ⁻⁴ mmol/μL) was mixed and heated with stirring at about 115° C. for about 1 hour.
22. Volatile matter (such as unreacted methyldimethoxysilane) was distilled off under reduced pressure to obtain a polymer [P2] having dimethoxysilyl groups at both ends of the molecule.

Polymer [P2] had a number average molecular weight of about 40,000 and a molecular weight distribution of 1.2. Polymer [P1] had an average of about 1.9 crosslinkable silyl groups per molecule.

[Preparation of sample for evaluation]
A sample for physical property evaluation was produced by the following procedure.
1. An aluminum substrate (width 25 mm, length 100 mm, thickness 2 mm) and glass partially shielded with aluminum tape (width 25 mm, length 100 mm, thickness 2 mm) were prepared.
2. The curable composition was applied to an aluminum substrate so as to have a thickness of 150 µm. A glass with an aluminum tape was attached to this coated surface to provide a bright portion directly irradiated with UV and a dark portion not irradiated with UV.
3. Using a UV irradiation device (manufactured by Fusion UV System, model: LIGHT HAMMER 6, light source: mercury lamp, peak illuminance: 250 mW/cm ² , integrated light intensity: 2,000 mJ/cm ² ), the glass surface is irradiated with UV. Then, a sample for evaluation was produced.

[Materials used in Examples and Comparative Examples]
- (Meth) acrylic acid ester polymer 1: the polymer synthesized in Synthesis Example 1 [P1]
- (Meth) acrylic acid ester polymer 2: the polymer synthesized in Synthesis Example 2 [P2]
・ Naphthoquinonediazide compound: 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride (manufactured by Tokyo Kasei)
Silane coupling agent: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (manufactured by MOMENTIVE, Siquest A-186 Silane)
- Polyether polymer: hydrolyzable silyl group-containing polypropylene oxide (manufactured by Kaneka, S203H)
・ Amine compound: 3-diethylaminopropylamine (manufactured by Fujifilm Wako Pure Chemical Industries)
Amine precursor compound: (Z)-{[bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methamiminidium tetrakis(3-fluorophenyl)borate (WPBG-345 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
- Organic acid: neodecanoic acid (manufactured by Hexion, Versatic Acid 10)
Photoacid generator: 50% propylene carbonate solution of triarylsulfonium/fluorophosphine salt (manufactured by San-Apro, CPI-200K)
[Method for evaluating physical properties]
[Curability and Curing Speed]
After a predetermined time had passed since the UV irradiation, the laminated aluminum tape-attached glass was peeled off, and the curable composition applied to the bright and dark areas was touched with a spatula. At this time, if the curable composition did not adhere to the spatula, it was judged to be "cured", and if it adhered, it was judged to be "not cured". Curability and curing speed were evaluated in the following five stages A to E (A is the fastest curing speed, and the closer to E, the slower the curing speed).
A: No adhesion immediately after UV irradiation.
B: No adhesion after 30 minutes of UV irradiation.
C: No adhesion after 1 hour of UV irradiation.
D: No adhesion 1 day after UV irradiation.
E: There is adhesion 1 day after UV irradiation.

[Adhesiveness]
After a predetermined time had passed since the UV irradiation, the laminated glass with aluminum tape was peeled off, and the curable composition applied to the bright and dark areas was rubbed with a spatula. If the curable composition did not peel off from the aluminum substrate, it was judged to be "adhered", and if it was peeled off, it was judged to be "non-adhered". Adhesiveness was evaluated in the following 6 stages from A to E (A is the highest adhesiveness, and the closer to E, the lower the adhesiveness).
A: No peeling after 30 minutes of UV irradiation.
B: No peeling after 1 hour of UV irradiation.
C: Not peeled off 1 day after UV irradiation.
D: Slightly peeled off 1 hour after UV irradiation.
E: Peeled off 1 day after UV irradiation.

[Example 1]
To 100 parts by weight of polymer [P1] was added 5 parts by weight of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride (added as a 10% by weight acetone solution). After stirring with a spatula, acetone was removed by vacuum devolatilization at 40°C. Further, using a planetary stirring and defoaming machine (model name: ARE-310, manufactured by Thinky), the mixture was stirred at 1600 rpm for 1.5 minutes and then defoamed at 2200 rpm for 3 minutes. Thus, a curable composition was obtained. Table 1 shows the results of evaluating physical properties.

[Examples 2 to 4]
A curable composition was obtained in the same manner as in Example 1, except that the amount of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride was changed. Table 1 shows the results of evaluating physical properties.

[Example 5]
A curable composition was obtained in the same manner as in Example 1, except that 1 part by weight of 3-diethylaminopropylamine was further added as the amine compound (VII). 3-diethylaminopropylamine was added after devolatilization of acetone. Table 1 shows the results of evaluating physical properties.

[Examples 6 to 9]
(Z)-{[bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methamiminidium tetrakis(3-fluorophenyl)borate was further blended as the amine precursor compound (VII-A), A curable composition was obtained in the same manner as in Example 1. (Z)-{[bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methamiminidium tetrakis(3-fluorophenyl)borate can be obtained by adding 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride After that, it was added as a 20 wt% acetone solution. Table 1 shows the results of evaluating physical properties.

[Example 10]
A curable composition was obtained in the same manner as in Example 6, except that 0.5 parts by weight of water was added. Water was added after devolatilization of acetone. Table 1 shows the results of evaluating physical properties.

[Example 11]
A curable composition was obtained in the same manner as in Example 10, except that 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was further added as the silane coupling agent (V). 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was added after devolatilization of acetone. Table 1 shows the results of evaluating physical properties.

[Example 12]
A curable composition was obtained in the same manner as in Example 10, except that the polymer [P1] was changed to the polymer [P2] and the polyether polymer (VI) was further blended. Table 1 shows the results of evaluating physical properties.

[Comparative Example 1]
Without blending the naphthoquinonediazide compound (II), 3 parts by weight of the amine precursor compound (VII-A) and 3 parts by weight of an organic carboxylic acid (neodecanoic acid) were blended as a curing catalyst, and 0.2 parts by weight as a curing accelerator component. 5 parts by weight of water were incorporated. Otherwise, a curable composition was obtained in the same manner as in Example 1. Table 1 shows the results of evaluating physical properties.

[Comparative Example 2]
A curable composition was obtained in the same manner as in Example 1, except that 2 parts by weight of a photoacid generator (trade name: CPI200K, manufactured by San-Apro) was added without blending the naphthoquinonediazide compound (II). Table 1 shows the results of evaluating physical properties.

[Comparative Example 3]
Without blending the naphthoquinone diazide compound (II), 5 parts by weight of the amine precursor compound (VII-A) and 2 parts by weight of an organic carboxylic acid (neodecanoic acid) were blended as a curing catalyst. Otherwise, a curable composition was obtained in the same manner as in Example 1. Table 1 shows the results of evaluating physical properties.

[Comparative Example 4]
Without blending the naphthoquinone diazide compound (II), 5 parts by weight of the amine precursor compound (VII-A) and 2 parts by weight of an organic carboxylic acid (neodecanoic acid) were blended as a curing catalyst, and 0.00 part as a curing accelerator component. 5 parts by weight of water were incorporated. Otherwise, a curable composition was obtained in the same manner as in Example 1. Table 1 shows the results of evaluating physical properties.

From Table 1, the system using the naphthoquinonediazide compound (II) as the photoacid generator exhibited excellent curability and adhesiveness in both the bright and dark areas. On the other hand, the system using a combination of an amine and a carboxylic acid as a curing catalyst (Comparative Examples 1, 3, and 4) and the system using a photoacid generator other than the naphthoquinonediazide compound (II) (Comparative Example 2) exhibited poor curability. and poor adhesiveness. Incidentally, the photoacid generator (triarylsulfonium/fluorophosphine salt) used in Comparative Example 2 is the same as the photoacid generator used in Examples of Patent Document 1.

Regarding the curability, it was found that when 2 parts by weight or more of the naphthoquinone diazide compound (II) was added to 100 parts by weight of the (meth)acrylic acid ester polymer, the curability was improved in both the light and dark areas. (see Examples 1-4).

One aspect of the present invention can be used in the field of curable compositions.

Claims (11)

a (meth)acrylic ester-based polymer (I) having an average of one or more crosslinkable silyl groups per molecule;
a naphthoquinone azide compound (II);
A curable composition comprising: 2. The curable composition of claim 1, further comprising water (III). 3. The curable composition according to claim 1, wherein the (meth)acrylate polymer (I) has a molecular weight distribution of less than 1.8. The curable composition according to any one of claims 1 to 3, wherein the crosslinkable silyl group is represented by the following general formula (1):
[Si(R ¹ ) _2-b (Y) _b O] _m -Si(R ² ) _3-a (Y) _a (1)
In formula (1),
R ¹ and R ² each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R′) ₃ SiO—. represents a triorganosiloxy group that is
when two or more of each of R ¹ or R ² are present, they may be the same or different;
R ' represents a monovalent hydrocarbon group having 1 to 20 carbon atoms,
Multiple R' may be the same or different,
Y represents a hydroxyl group or a hydrolyzable group,
when two or more Y are present, they may be the same or different;
a represents an integer of 0, 1, 2 or 3,
b represents an integer of 0, 1, or 2;
m represents an integer from 0 to 19,
satisfies a+mb≧1. 5. The curable composition according to any one of claims 1 to 4, wherein the crosslinkable silyl group of the (meth)acrylic acid ester polymer (I) is present at the molecular chain terminal. A curable composition according to any one of claims 1 to 5, further comprising an epoxy resin (IV). The curable composition according to any one of claims 1 to 6, further comprising a silane coupling agent (V). The curable composition according to any one of claims 1 to 7, further comprising a polyether polymer (VI) having one or more crosslinkable silyl groups per molecule on average. The curable composition according to any one of claims 1 to 8, further comprising an amine compound (VII). The curable composition according to any one of claims 1 to 8, further comprising an amine precursor compound (VII-A) that generates an amine compound upon irradiation with light. A cured product obtained by curing the curable composition according to any one of claims 1 to 10.