Curable composition and cured product

Abstract

To provide a curable composition having improved adhesion.SOLUTION: A curable composition contains: a (meth)acrylic polymer (A) having trialkoxysilyl groups at or near an end of the molecular chain, the number of the trialkoxysilyl groups being 1.0 or more on average per molecule; a (meth)acrylic polymer (B) having (meth)acryloyl groups at an end of the molecular chain, the number of the (meth)acryloyl groups being 1.0 or more on average per molecule, a photoradical polymerization initiator (C), and a condensation catalyst (D).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to curable compositions and cured products. The present invention also relates to flat panel displays and conformal coatings comprising the cured products. [Background technology]

[0002] 2. Description of the Related Art Conventionally, curable compositions containing a (meth)acrylic polymer that is cured by irradiation with light and a (meth)acrylic polymer that is cured in reaction with moisture are known (Patent Documents 1, 2, etc.). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2012-136685 A [Patent Document 2] JP 2019-143014 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, the above-mentioned conventional techniques leave room for improvement in terms of adhesion (eg, adhesion to glass).

[0005] One aspect of the present invention aims to provide a curable composition having improved adhesion. [Means for solving the problem]

[0006] In order to solve the above problems, a curable composition according to one aspect of the present invention comprises: A (meth)acrylic polymer (A) having an average of 1.0 or more trialkoxysilyl groups per molecule at or near the terminals of the molecule; A (meth)acrylic polymer (B) having an average of 1.0 or more (meth)acryloyl groups per molecule at the molecular terminals; A photoradical polymerization initiator (C); A condensation catalyst (D); Contains: Effect of the Invention

[0007] According to one aspect of the present invention, there is provided a curable composition having improved adhesion properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Hereinafter, an example of an embodiment of the present invention will be described in detail, but the present invention is not limited to this.

[0009] Unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more and B or less." In this specification, "(meth)acrylic" means "acrylic" and / or "methacrylic".

[0010] <<A. Curable composition>> The curable composition according to one embodiment of the present invention contains a (meth)acrylic polymer (A) having a trialkoxysilyl group at or near at least one end of the molecule, a (meth)acrylic polymer (B) having a (meth)acryloyl group at at least one end of the molecule, a photoradical polymerization initiator (C), and a condensation catalyst (D). The curable composition may contain an optional component, a (meth)acrylic monomer (E), a silane coupling agent (F), and other additives. Each component will be described in detail below.

[0011] [A1. (Meth)acrylic polymer (A)] The (meth)acrylic polymer (A) has an average of 1.0 or more trialkoxysilyl groups per molecule at or near the terminals of the molecule. The "near the terminals of the molecule" can be, for example, a region in which 40% or less, 30% or less, or 25% or less of the repeating units are located, counting from the terminals of the molecule, assuming that the total number of repeating units contained in the molecule is 100%. Since a linear molecule has two terminals, there are also two terminal vicinities.

[0012] In one embodiment, the (meth)acrylic polymer (A) has a trialkoxysilyl group near at least one end of the molecule. One or more trialkoxysilyl groups may be present in one end-near region. Thus, the molecule as a whole has one or more trialkoxysilyl groups, and may have more than two trialkoxysilyl groups. Such a polymer can be produced, for example, by the first aspect of the production method described in Section [A1.4]. According to this production method, the (meth)acrylic polymer (A1) described below can be obtained.

[0013] In one embodiment, the (meth)acrylic polymer (A) has trialkoxysilyl groups near both ends of the molecule. One or more trialkoxysilyl groups may be present in one terminal vicinity region. Thus, the molecule as a whole has two or more trialkoxysilyl groups, and may have more than two trialkoxysilyl groups. Such a polymer can be produced, for example, by the first aspect of the production method described in Section [A1.4]. According to this production method, the (meth)acrylic polymer (A1) described below can be obtained.

[0014] In one embodiment, the (meth)acrylic polymer (A) has a trialkoxysilyl group at at least one end of the molecule. Therefore, the molecule as a whole has one or two trialkoxysilyl groups. Such a polymer can be produced, for example, by the second aspect of the production method described in Section [A1.4].

[0015] In one embodiment, the (meth)acrylic polymer (A) has trialkoxysilyl groups at both ends of the molecule. Therefore, the molecule as a whole has two trialkoxysilyl groups. Such a polymer can be produced, for example, by the second aspect of the production method described in Section [A1.4].

[0016] In one embodiment, the (meth)acrylic polymer (A) has a trialkoxysilyl group both near at least one end of the molecule and in a region other than the end of the molecule. In one embodiment, the (meth)acrylic polymer (A) has a trialkoxysilyl group at at least one end of the molecule, and has no trialkoxysilyl group in a region other than the end of the molecule.

[0017] The number of trialkoxysilyl groups introduced into the (meth)acrylic polymer (A) is 1.0 or more on average in the whole molecule. In one embodiment, the number of trialkoxysilyl groups introduced into the (meth)acrylic polymer (A) is more than 1.0 on average in the whole molecule. In one embodiment, the number of trialkoxysilyl groups is preferably 1.1 or more, more preferably 1.2 or more. In another embodiment, the number of trialkoxysilyl groups is preferably 2.2 or more, more preferably 2.4 or more. The upper limit of the number of trialkoxysilyl groups introduced into the (meth)acrylic polymer (A) is preferably 10.0 or less, more preferably 8.0 or less, and even more preferably 6.0 or less. If the number of trialkoxysilyl groups is within the above range, the physical properties of the curable composition and the cured product using the (meth)acrylic polymer (A) are good. In addition, it is preferable that the (meth)acrylic polymer (A) has trialkoxysilyl groups at both ends (or terminal regions) of the molecule.

[0018] In one embodiment, the number average molecular weight of the (meth)acrylic polymer (A) is preferably 4,000 to 80,000, more preferably 10,000 to 50,000. If the number average molecular weight is 4,000 or more, the properties of the (meth)acrylic polymer (A) can be fully exhibited. If the number average molecular weight is 80,000 or less, the viscosity does not become too high, and sufficient workability can be ensured. The number average molecular weight can be measured, for example, by gel permeation chromatography (GPC).

[0019] In one embodiment, the molecular weight distribution of the (meth)acrylic polymer (A) is 1.8 or less. The molecular weight distribution of the (meth)acrylic polymer (A) is preferably 1.7 or less, more preferably 1.6 or less, even more preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less. If the molecular weight distribution is too large, the viscosity of the curable composition increases, and the workability tends to decrease.

[0020] The weight average molecular weight and number average molecular weight can be measured, for example, by gel permeation chromatography (GPC). For GPC measurement, chloroform can be used as the mobile phase and a polystyrene gel column can be used as the stationary phase. These molecular weights can be calculated in terms of polystyrene.

[0021] The (meth)acrylic polymer (A) having such a narrow molecular weight distribution can be suitably produced, for example, by living radical polymerization.

[0022] [A1.1. (Meth)acrylic acid ester monomers] The (meth)acrylic polymer (A) according to one embodiment of the present invention contains a repeating unit derived from a (meth)acrylic acid ester monomer. The (meth)acrylic acid ester monomer that is the raw material of the (meth)acrylic polymer (A) is not particularly limited. Only one type of (meth)acrylic acid ester monomer may be used, or two or more types of (meth)acrylic acid ester monomers may be used in combination.

[0023] Examples of such (meth)acrylic acid ester monomers include the following: (Meth)acrylic acid ester monomer (α): a monomer having an alkyl group ester-bonded to (meth)acrylic acid, and the alkyl group having an alkoxy group having a carbon number of 1 to 5. The number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 2. The number of carbon atoms in the alkoxy group is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1. (Meth)acrylic acid ester monomer (β): A monomer having 1 to 5 carbon atoms in the alkyl group that is ester-bonded to (meth)acrylic acid. (Meth)acrylic acid ester monomer (γ): A monomer having 6 to 15 carbon atoms in the alkyl group that is ester-bonded to (meth)acrylic acid. (Meth)acrylic acid ester monomer (δ): A monomer having 16 to 25 carbon atoms in the alkyl group that is ester-bonded to (meth)acrylic acid.

[0024] In one embodiment, the (meth)acrylic polymer (A) has a preferred monomer composition as follows. The following ratios are based on the weight of all repeating units contained in the (meth)acrylic polymer (A). Such a monomer composition allows the (meth)acrylic polymer (A) to have good workability, mechanical properties, and weather resistance. Repeating units derived from a (meth)acrylic acid ester monomer (α): preferably 0 to 20% by weight. · The total of repeating units derived from the (meth)acrylic acid ester monomer (β) and the (meth)acrylic acid monomer (γ): preferably 45 to 96% by weight. Repeating units derived from a (meth)acrylic acid ester monomer (δ): preferably 4 to 35% by weight.

[0025] In one embodiment, the preferred monomer composition of the (meth)acrylic polymer (A) is as follows. The following proportions are based on the weight of all repeating units contained in the (meth)acrylic polymer (A). With such a monomer composition, the viscosity of the (meth)acrylic polymer (A) can be further reduced, resulting in further improved workability. Repeating units derived from a (meth)acrylic acid ester monomer (α): preferably from 5 to 20% by weight, more preferably from 10 to 20% by weight. · Repeating units derived from a (meth)acrylic acid ester monomer (β): preferably from 45 to 70% by weight, more preferably from 50 to 70% by weight. · Repeating units derived from a (meth)acrylic acid ester monomer (γ): preferably from 0 to 25% by weight, more preferably from 10 to 25% by weight. · Repeating units derived from a (meth)acrylic acid ester monomer (δ): preferably from 15 to 25% by weight, more preferably from 15 to 20% by weight.

[0026] If the content of the repeating unit derived from the (meth)acrylic acid ester monomer (β) is within the above range, a curable composition having low viscosity and good workability can be obtained. If the content of the repeating unit derived from the (meth)acrylic acid ester monomer (γ) is within the above range, a cured product having excellent durability can be obtained. If the content of the repeating unit derived from the (meth)acrylic acid ester monomer (δ) is within the above range, a cured product having excellent mechanical properties can be obtained.

[0027] The (meth)acrylic acid ester monomer is not particularly limited, and conventionally known monomers can be used. Examples of the (meth)acrylic acid ester monomer (α) include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, and isopropoxyethyl (meth)acrylate. Examples of the (meth)acrylic acid ester monomer (β) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl (meth)acrylate. Examples of the (meth)acrylic acid ester monomer (γ) include n-hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, and tetradecyl (meth)acrylate. Examples of the (meth)acrylic acid ester monomer (δ) include pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, icosyl (meth)acrylate, and docosyl (meth)acrylate.

[0028] Among the above-mentioned monomers, the (meth)acrylic acid ester monomer (α) is preferably 2-methoxyethyl acrylate. The (meth)acrylic acid ester monomer (β) is preferably butyl acrylate. The (meth)acrylic acid ester monomer (γ) is preferably 2-ethylhexyl acrylate and dodecyl acrylate. The (meth)acrylic acid ester monomer (δ) is preferably octadecyl acrylate. By selecting these monomers, the (meth)acrylic polymer (A) produced can achieve high levels of viscosity, weather resistance, mechanical properties, and durability in a well-balanced manner.

[0029] In one embodiment, the (meth)acrylic acid ester monomer (α) is: (a) and / or (b): (a) A monomer having 1 to 5 carbon atoms in an alkyl group bonded to (meth)acrylic acid via an ester bond, provided that the "number of carbon atoms in the alkyl group" does not include the carbon atoms contained in the alkoxy group of the alkyl group. (b) one or more monomers selected from the group consisting of 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, and isopropoxyethyl (meth)acrylate.

[0030] In one embodiment, the (meth)acrylic polymer (A) has a repeating unit derived from n-butyl acrylate. The content of the repeating unit derived from n-butyl acrylate is preferably 50% by weight or more, more preferably 70% by weight or more, and even more preferably 90% by weight or more, based on the weight of all repeating units contained in the (meth)acrylic polymer (A). By using such a (meth)acrylic polymer (A), a curable composition having low viscosity and good workability can be obtained.

[0031] The repeating units derived from the (meth)acrylic ester monomer contained in the (meth)acrylic polymer (A) are preferably 70% by weight or more, more preferably 90% by weight or more, based on all the repeating units contained in the polymer (A). If the content of the repeating units derived from the (meth)acrylic ester monomer is 70% or more, the produced (meth)acrylic polymer (A) has good weather resistance, mechanical properties and durability.

[0032] [A1.2. Trialkoxysilyl group] The (meth)acrylic polymer (A) has a trialkoxysilyl group. In one embodiment, the trialkoxysilyl group is represented by the following general formula (1). -[Si(R 1 ) 2-a (Y) a O] m -Si(Y) 3 (1).

[0033] In the formula, R 1 is 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, a methoxymethyl group, or (R') 3 It is a triorganosiloxy group represented by SiO- (wherein R' is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R's may be the same or different). 1 When there are two or more R 1 may be the same or different. Y is an alkoxy group having 1 to 20 carbon atoms (the three Y's may be the same or different). a is 0, 1 or 2. m is an integer of 0 to 19.

[0034] In one embodiment, the trialkoxysilyl group of the (meth)acrylic polymer (A) is a trimethoxysilyl group. By selecting a trimethoxysilyl group, the curability of the curable composition is improved. In this embodiment, the (meth)acrylic polymer (A) may or may not have a trialkoxysilyl group other than the trimethoxysilyl group.

[0035] In general, the fewer the carbon number of an alkoxy group, the higher the reactivity. That is, the reactivity decreases in the order of methoxy group, ethoxy group, propoxy group, etc. Therefore, an appropriate alkoxy group can be selected depending on the production method and application of the (meth)acrylic polymer (A).

[0036] For example, the trialkoxysilyl group can be introduced as a (meth)acrylic acid ester monomer having a trialkoxysilyl group. The specific structure of the (meth)acrylic acid ester monomer having a trialkoxysilyl group is not particularly limited. One example is a monomer represented by the following general formula (2). H 2 C=CR 2 C(=O)O-(CH 2 ) m -Si(OR 3 ) 3 (2).

[0037] In the formula, R 2 is hydrogen or a methyl group. 3 is at least one selected from the group consisting of a methyl group and an ethyl group. 3 is independently selected. m is an integer from 1 to 10.

[0038] Specific examples of the (meth)acrylic acid ester monomer having a trialkoxysilyl group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

[0039] [A1.3. (Meth)acrylic polymer (A1)] In one embodiment, the (meth)acrylic polymer (A) has an X block and a Y block, and contains an XY diblock structure or an XYX triblock structure in the molecule. In this specification, such a (meth)acrylic polymer is referred to as a (meth)acrylic polymer (A1). The structure of the entire molecule of the (meth)acrylic polymer (A1) is not particularly limited as long as it contains an XY diblock structure or an XYX triblock structure, and may be, for example, an XYXY tetrablock structure.

[0040] Here, the term "XYX triblock structure" refers to what is generally known by those skilled in the art as an "ABA triblock structure." The ratio of X / Y in the XY diblock structure and the XYX triblock structure is preferably from (5 / 95) to (60 / 40), more preferably from (15 / 85) to (40 / 60).

[0041] In one embodiment, the molecule of the (meth)acrylic polymer (A1) has an XY diblock structure. In the molecule of the XY diblock structure, the X block may be a region in which 40% or less, 30% or less, or 25% or less of the repeating units are located, counting from the terminal of the molecule, with the total number of repeating units contained in the molecule being 100%. Here, the X block is a block on the side where trialkoxysilyl groups are distributed in a relatively large amount.

[0042] In one embodiment, the molecule of the (meth)acrylic polymer (A1) has an XYX triblock structure. In the molecule of the XYX triblock structure, the X block can be a region in which 40% or less, 30% or less, or 25% or less of the repeating units are located, counting from the terminals of the molecule, with the total number of repeating units contained in the molecule being 100%. Here, the X blocks are blocks located at both terminals of the molecule.

[0043] In one embodiment, the (meth)acrylic polymer (A1) has a repeating unit derived from a (meth)acrylic acid ester monomer having a trialkoxysilyl group. The repeating unit derived from the (meth)acrylic acid ester monomer having a trialkoxysilyl group is contained relatively more in the X block. Specifically, the repeating unit derived from the (meth)acrylic acid ester monomer having a trialkoxysilyl group contained in the X block is 1.0 or more on average. On the other hand, the repeating unit derived from the (meth)acrylic acid ester monomer having a trialkoxysilyl group contained in the Y block is 0 to 3% by weight based on the weight of all repeating units contained in the Y block. Therefore, the repeating unit derived from the (meth)acrylic acid ester monomer having a trialkoxysilyl group is localized near the terminal in the (meth)acrylic polymer (A1).

[0044] The repeating units derived from the (meth)acrylic acid ester monomer having a trialkoxysilyl group contained in the X block are preferably 1.5 or more, more preferably 1.7 or more, on average. Similarly, the repeating units derived from the (meth)acrylic acid ester monomer having a trialkoxysilyl group contained in the X block are preferably more than 3% by weight, more preferably 4.5% by weight or more, and even more preferably 5% by weight or more, based on the weight of all repeating units contained in the X block. The upper limit of the repeating units derived from the (meth)acrylic acid ester monomer having a trialkoxysilyl group contained in the Y block is preferably 2% by weight or less, more preferably 1% by weight or less, based on the weight of all repeating units contained in the Y block. The lower limit of the repeating units derived from the (meth)acrylic acid ester monomer having a trialkoxysilyl group contained in the Y block is preferably more than 0% by weight, more preferably 0% by weight or more, based on the weight of all repeating units contained in the Y block.

[0045] In one embodiment, the number of trialkoxysilyl groups introduced into the (meth)acrylic polymer (A1) is different between the X block and the Y block, as described above. When the (meth)acrylic polymer (A1) has an XY diblock structure, the average number of trialkoxysilyl groups introduced into the entire molecule is 1 or more, preferably 1.1 or more, more preferably 1.2 or more. When the (meth)acrylic polymer (A1) has an XYX triblock structure or an XYXY tetrablock structure, the average number of trialkoxysilyl groups introduced into the entire molecule is 2 or more, preferably 2.2 or more, more preferably 2.4 or more. The upper limit of the number of trialkoxysilyl groups introduced into the (meth)acrylic polymer (A1) is preferably 10.0 or less, more preferably 8.0 or less, and even more preferably 6.0 or less. If the number of trialkoxysilyl groups is within the above range, the physical properties of the curable composition and the cured product using the (meth)acrylic polymer (A1) are good.

[0046] In one embodiment, the (meth)acrylic polymer (A1) has more than 2.0 trialkoxysilyl groups on average per molecule. This is because in the (meth)acrylic polymer (A1), two or more trialkoxysilyl groups can be introduced into one X block, and also because a trialkoxysilyl group can be introduced into the Y block. Therefore, the (meth)acrylic polymer (A1) has two or more trialkoxysilyl groups regardless of the block structure. The number of trialkoxysilyl groups that the (meth)acrylic polymer (A1) has is more preferably 2.2 or more, and even more preferably 2.4 or more, on average per molecule. The number of trialkoxysilyl groups that the (meth)acrylic polymer (A1) has is preferably 10.0 or less, more preferably 8.0 or less, and even more preferably 6.0 or less, on average per molecule.

[0047] Thus, the (meth)acrylic polymer (A1) is preferred in that a large number of trialkoxysilyl groups can be introduced. Since the trialkoxysilyl groups become reaction points for forming crosslinks, the more trialkoxysilyl groups contained in the polymer, the more the adhesiveness can be improved. However, if the number of trialkoxysilyl groups becomes too large, the storage stability of the curable composition may decrease. Therefore, the trialkoxysilyl groups contained in the (meth)acrylic polymer (A1) are preferably within the above range.

[0048] [A1.4. Method for producing (meth)acrylic polymer (A)] The polymerization method of the (meth)acrylic polymer (A) is not particularly limited, and known polymerization methods can be used (radical polymerization method, cationic polymerization method, anionic polymerization method, etc.). Among them, living polymerization method is preferred because it can introduce a functional group to the end of the polymer molecule and can synthesize an XY block polymer or an XYX block polymer. Examples of living polymerization methods include living radical polymerization method, living cationic polymerization method, and living anionic polymerization method, and among them, living radical polymerization method is suitable for polymerization of acrylic acid ester monomers. Examples of living radical polymerization methods include the following. Atom Transfer Radical Polymerization (ATRP) (see J. Am. Chem. Soc. 1995, 117, 5614; Macromolecules. 1995, 28, 1721) ·Sigle Electron Transfer Polymerization; SET-LRP (J. Am. Chem. Soc. 2006, 128, 14156; JPSChem 2007, 45, 1607) Reversible Chain Transfer Catalyzed Polymerization (RTCP) ("Living Radical Polymerization Controlled by Organic Catalysts" Polymer Journal 68, 223-231 (2011); See JP 2014-111798) Reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) Nitroxy radical method (NMP method) ·Organotellurium Polymerization (TERP) method ·Organoantimony Polymerization Method (SBRP Method) ·Organobismuth Polymerization Method (BIRP) -Iodine transfer polymerization method.

[0049] Hereinafter, two specific examples of the method for producing the (meth)acrylic polymer (A) will be described. Among these examples, according to the first embodiment, the (meth)acrylic polymer (A1) can be produced.

[0050] (First aspect) In one embodiment, the (meth)acrylic polymer (A) can be produced by a production method including the following steps 1a and 2a, or the following steps 1b and 2b. Since this production method produces a block copolymer, the resulting (meth)acrylic polymer (A) is a (meth)acrylic polymer (A1). The (meth)acrylic polymer (A1) produced by this production method is preferable in that the viscosity of the polymer is reduced.

[0051] In the following description, "containing 0% by weight of a (meth)acrylic acid ester monomer having a trialkoxysilyl group" means "containing no (meth)acrylic acid ester monomer having a trialkoxysilyl group".

[0052] (Step 1a) A step of polymerizing a (meth)acrylic acid ester monomer mixture containing a (meth)acrylic acid ester monomer having a trialkoxysilyl group (preferably more than 3% by weight) using a living polymerization initiator.

[0053] (Step 2a) A step of adding a (meth)acrylic acid ester monomer mixture containing 0 to 3% by weight of a (meth)acrylic acid ester monomer having a trialkoxysilyl group to the reaction system after step 1a, and polymerizing the mixture.

[0054] (Step 1b) A step of polymerizing a (meth)acrylic acid ester monomer mixture containing 0 to 3% by weight of a (meth)acrylic acid ester monomer having a trialkoxysilyl group by using a living polymerization initiator.

[0055] (Step 2b) A step of adding a (meth)acrylic acid ester monomer mixture containing a (meth)acrylic acid ester monomer having a trialkoxysilyl group (preferably more than 3% by weight) to the reaction system after step 1b and polymerizing the mixture.

[0056] Hereinafter, each step will be described in more detail for each structure of the (meth)acrylic polymer (A1).

[0057] (When the polymer has an XY diblock structure) The (meth)acrylic polymer (A1), which is a molecule having an XY diblock structure, can be produced by the above-mentioned steps 1a and 2a, or steps 1b and 2b. In this case, steps 1a and 2b form an X block containing a relatively large amount of trialkoxysilyl groups. On the other hand, steps 2a and 1b form a Y block containing a relatively small amount of trialkoxysilyl groups.

[0058] In step 1a, a (meth)acrylic acid ester monomer having a trialkoxysilyl group is polymerized by a living polymerization initiator. As the living polymerization initiator, for example, an initiator having one halogen group in the molecule can be used. The amount of the (meth)acrylic acid ester monomer having a trialkoxysilyl group can be 1 to 10 molar equivalents relative to 1 molar equivalent of the initiator. In addition, 1 to 100 molar equivalents of a (meth)acrylic acid ester monomer not having a trialkoxysilyl group may be polymerized together, if necessary. Preferably, the amount of the (meth)acrylic acid ester monomer having a trialkoxysilyl group added to the reaction system in step 1a accounts for more than 3% by weight of the monomer mixture added to the reaction system in step 1a.

[0059] In step 2a, a (meth)acrylic acid ester monomer having no trialkoxysilyl group is added to the reaction system after step 1a to polymerize it. The amount of the (meth)acrylic acid ester monomer having no trialkoxysilyl group added may be 2 to 600 molar equivalents per molar equivalent of the polymer obtained in step 1a. In step 2a, a (meth)acrylic acid ester monomer having a trialkoxysilyl group may be added to the reaction system. The amount of the (meth)acrylic acid ester monomer having a trialkoxysilyl group added to the reaction system in step 2a accounts for 0 to 3 weight % of the monomer mixture added to the reaction system in step 2a.

[0060] In step 1b, a (meth)acrylic acid ester monomer having no trialkoxysilyl group is polymerized by a living polymerization initiator. The same living polymerization initiator as in step 1a can be used. The amount of the (meth)acrylic acid ester monomer having no trialkoxysilyl group can be 2 to 600 molar equivalents per molar equivalent of the initiator. In step 1b, a (meth)acrylic acid ester monomer having a trialkoxysilyl group may be added to the reaction system. The amount of the (meth)acrylic acid ester monomer having a trialkoxysilyl group added to the reaction system in step 1b accounts for 0 to 3% by weight of the monomer mixture added to the reaction system in step 1b.

[0061] In step 2b, a (meth)acrylic acid ester monomer having a trialkoxysilyl group is added to the reaction system after step 1b and polymerized. The amount of the (meth)acrylic acid ester monomer having a trialkoxysilyl group can be 1 to 10 molar equivalents relative to 1 molar equivalent of the polymer obtained in step 1b. If necessary, 1 to 100 molar equivalents of a (meth)acrylic acid ester monomer not having a trialkoxysilyl group may be polymerized together. Preferably, the amount of the (meth)acrylic acid ester monomer having a trialkoxysilyl group added to the reaction system in step 2b accounts for more than 3% by weight of the monomer mixture added to the reaction system in step 2b.

[0062] In the above process, examples of the "(meth)acrylic acid ester monomer having no trialkoxysilyl group" include the (meth)acrylic acid ester monomers (α), (β), (γ), and (δ) described in Section [1.1.]. This also applies to the following description.

[0063] (When the polymer has an XYX triblock structure) The (meth)acrylic polymer (A1), which is a molecule having an XYX triblock structure, can be produced by carrying out the additional polymerization step (a) after the above-mentioned steps 1a and 2a. At this time, the X block containing a relatively large amount of trialkoxysilyl groups is formed by the step 1a and the additional polymerization step (a). For this production method, the description in JP-A-2018-162394 can be referred to.

[0064] In the additional polymerization step (a), a (meth)acrylic acid ester monomer having a trialkoxysilyl group is added to the reaction system after step 2a and polymerized. The amount of the (meth)acrylic acid ester monomer having a trialkoxysilyl group added can be 1 to 10 molar equivalents relative to 1 molar equivalent of the polymer obtained in step 2a. If necessary, 1 to 100 molar equivalents of a (meth)acrylic acid ester monomer not having a trialkoxysilyl group may be polymerized together. Preferably, the amount of the (meth)acrylic acid ester monomer having a trialkoxysilyl group added to the reaction system in the additional polymerization step (a) accounts for more than 3% by weight of the monomer mixture added to the reaction system in the step.

[0065] (When the polymer has four or more blocks) By appropriately combining the above-mentioned steps 1a, 2a, 1b, 2b and an additional polymerization step, a (meth)acrylic polymer (A1) having four or more blocks can be produced. For example, a (meth)acrylic polymer (A1) having an XYXY tetrablock structure can be produced.

[0066] When the production method according to the first aspect is employed, halogen atoms may remain at one or both ends (the molecular extension terminals at the time of polymerization) of the (meth)acrylic polymer (A1). In one embodiment, the (meth)acrylic polymer (A1) has, on average, one or more halogen atoms per molecular extension terminal at the time of polymerization.

[0067] (Identification of the structure of the (meth)acrylic polymer (A) by the production method) In one embodiment, the (meth)acrylic polymer (A) is defined as a polymer obtained by the above-mentioned production method. That is, the (meth)acrylic polymer (A) can be a polymer obtained by a production method including steps 1a and 2a, or steps 1b and 2b.

[0068] In the above-mentioned production method, a (meth)acrylic acid ester monomer having a trialkoxysilyl group is introduced by copolymerization, so it is almost impractical to specifically specify the position of the trialkoxysilyl group in the resulting polymer molecule.

[0069] In the above-mentioned production method, when the same type of (meth)acrylic acid ester monomer not having a trialkoxysilyl group is added to the reaction system in steps 1a and 2a (or steps 1b and 2b), the main chain structure of the obtained polymer will be the same for both the X block and the Y block. In such a polymer, it is almost impractical to specifically specify the boundary between the X block and the Y block.

[0070] Due to these circumstances, there are cases where the (meth)acrylic polymer (A) must be defined not as a specific structure of a polymer molecule, but as a polymer obtained by the above-mentioned production method.

[0071] (Second aspect) In one example, the (meth)acrylic polymer (A) is produced by the method described in JP 2007-302749 A. Among them, the method of adding a hydrosilane compound having a trialkoxysilyl group to a (meth)acrylic polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst is preferred in terms of easier control.

[0072] In this method, a trialkoxysilyl group is introduced into a (meth)acrylic polymer as follows. 1. (Meth)acrylic acid ester monomers are subjected to living radical polymerization to obtain (meth)acrylic polymers. 2. The (meth)acrylic polymer obtained in 1 is reacted with a compound (diene compound) having at least two alkenyl groups with low polymerizability to obtain a vinyl polymer having at least one alkenyl group. 3. A hydrosilane compound having a trialkoxysilyl group is added to the vinyl polymer obtained in 2 in the presence of a hydrosilylation catalyst.

[0073] More specifically, the above-mentioned step 2 is carried out by reacting a diene compound (1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, etc.) at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer in the production of a (meth)acrylic polymer by living radical polymerization.

[0074] The hydrosilane compound having a trialkoxysilyl group is not particularly limited, and a representative example is a compound represented by the general formula (3). H-[Si(R 4 ) 2-a (Y) a O] m -Si(Y) 3 (3).

[0075] In general formula (3), R 4 each independently represents 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, a methoxymethyl group, or (R') 3 (wherein R' is a monovalent hydrocarbon group having 1 to 20 carbon atoms. The three R's may be the same or different.) 4 When two or more are present, they may be the same or different. Y represents an alkoxy group having 1 to 20 carbon atoms. a represents 0, 1, 2 or 3.

[0076] Among these hydrosilane compounds, the compound represented by the following general formula (4) is preferred from the viewpoint of easy availability. H-Si(Y) 3 (4).

[0077] In the general formula (4), Y is as defined above.

[0078] A transition metal catalyst is usually used when adding a hydrosilane compound having a trialkoxysilyl group to an alkenyl group. Examples of transition metal catalysts include platinum-based catalysts. More specifically, they include platinum alone; solid platinum dispersed on a support (alumina, silica, carbon black, etc.); chloroplatinic acid; complexes of chloroplatinic acid with alcohols, aldehydes, ketones, etc.; platinum-olefin complexes; and platinum(0)-divinyltetramethyldisiloxane complexes. Examples of catalysts other than platinum-based catalysts include RhCl(PPh 3 ) 3 , RhCl 3 , RuCl 3 , IrCl 3 , FeCl 3 , AlCl 3 , PdCl 2 H 2 O, NiCl 2 , TiCl 4 Examples include:

[0079] (Comparison between the first and second aspects) Comparing the first and second aspects of the production method, the first aspect is more preferable. There are two main reasons for this. First, the production method according to the first aspect allows two or more trialkoxysilyl groups to be introduced into the (meth)acrylic polymer. In contrast, the production method according to the second aspect allows the maximum number of alkoxysilyl groups to be introduced into the (meth)acrylic polymer to be two. From the viewpoint of adhesiveness, it is preferable that the (meth)acrylic polymer (A) has a larger number of alkoxysilyl groups.

[0080] Secondly, the production method according to the first aspect is easier to apply to mass production. In the production method according to the first aspect, a trialkoxysilyl group is introduced by utilizing an acrylic acid ester monomer having a trialkoxysilyl group. In contrast, in the production method according to the second aspect, a trialkoxysilyl group is introduced by utilizing a hydrosilane compound having a trialkoxysilyl group. An acrylic acid ester monomer having a trialkoxysilyl group is relatively easier to obtain and tends to be more chemically stable than a hydrosilane compound having a trialkoxysilyl group.

[0081] For these reasons, the (meth)acrylic polymer (A1) which can be produced by the production method according to the first embodiment is a preferred embodiment of the present invention.

[0082] (General matters regarding living radical polymerization) All of the above-mentioned production methods can be suitably carried out by adopting living radical polymerization techniques, among which atom transfer radical polymerization, single electron transfer polymerization, and reversible transfer catalytic polymerization are preferred.

[0083] More preferred production methods include living radical polymerization of vinyl monomers using ATRP or SET-LRP with transition metals or transition metal complexes (composed of transition metal compounds and ligands) as catalysts, and RTCP, which does not use transition metals as catalysts.

[0084] There are currently two interpretations of the mechanism of living radical polymerization catalyzed by transition metal complexes: ATRP and SET-LRP. Based on ATRP, living radical polymerization consists of the equilibrium of the following two reactions (as an example, we will explain using a copper complex): (a) The monovalent copper complex abstracts the halogen at the end of the polymer to generate a radical, thereby becoming a divalent copper complex. (b) The divalent copper complex adds a halogen to the radical at the polymer end to form a monovalent copper complex.

[0085] On the other hand, when interpreted based on the SET LRP, living radical polymerization consists of the equilibrium of the following three reactions (as an example, we will explain using a copper complex): (a) Zero-valent metallic copper or a copper complex abstracts a halogen atom at the end of a polymer to generate a radical, thereby becoming a divalent copper complex. (b) The divalent copper complex adds a halogen to the radical at the polymer end to become a zerovalent copper complex. (c) The monovalent copper complex disproportionates to give zero- and divalent copper complexes.

[0086] The above-mentioned production method can be interpreted as any living radical polymerization system, but the present invention does not particularly distinguish between the two. Any living radical polymerization system using a transition metal or a transition metal compound and a ligand as a catalyst is included in the scope of the present invention.

[0087] In addition, Activators Regenerated by Electron Transfer (ARGET), a synthetic method that improves ATRP, has also been reported (Macromolecules. 2006, 39, 39). This method uses a reducing agent to reduce highly oxidized transition metal complexes that cause polymerization delays or terminations, and can rapidly progress the polymerization reaction to a high reaction rate even under low catalyst conditions with a small amount of transition metal complex. This ARGET can also be used in the present invention.

[0088] Various chemicals that can be used in the manufacturing method according to one embodiment of the present invention will be described below. Each of these chemicals may be used alone or in combination of two or more. These chemicals may be added directly to the polymerization system, or may be generated within the polymerization system.

[0089] (a. Initiator) As the initiator, a radical initiator having one halogen group in the molecule can be used. Examples of such initiators include ethyl 2-bromoisobutyrate, ethyl 2-bromobutyrate (also called ethyl α-bromobutyrate), ethyl bromoacetate, methyl bromoacetate, (1-bromoethyl)benzene, allyl bromide, methyl 2-bromopropionate, methyl chloroacetate, methyl 2-chloropropionate, and (1-chloroethyl)benzene.

[0090] From the viewpoint of easy availability, ethyl 2-bromobutyrate, (1-bromoethyl)benzene, and methyl chloroacetate are preferred, and from the viewpoints of reactivity and safety, ethyl 2-bromobutyrate is preferred.

[0091] Also, an initiator having a trialkoxysilyl group may be used as the initiator. Alternatively, a trialkoxysilyl group may be introduced into the initiator before or after the polymerization reaction. By such a method, the (meth)acrylic polymer (A) having a trialkoxysilyl group at least at the terminal can be produced.

[0092] (b. Polymerization catalyst) In the ATRP system, whether or not a reducing agent is used, a metal complex having a central metal of an element of Group 7, 8, 9, 10, or 11 of the periodic table can be used. Among these, metal complexes having a central metal of monovalent copper, divalent ruthenium, or divalent iron are particularly suitable.

[0093] Specific examples include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous acetate, and cuprous perchlorate. When a copper compound is used as a polymerization catalyst, it is preferable to add an amine ligand to the polymerization system in order to increase the catalytic activity. In addition, tristriphenylphosphine complexes of divalent ruthenium chloride (RuCl 2 (PPh 3 ) 3) is also suitable as a catalyst. When using this catalyst, it is preferable to add an aluminum compound (such as trialkoxyaluminum) to the polymerization system in order to enhance the catalytic activity. Furthermore, a tristriphenylphosphine complex of divalent iron chloride (FeCl 2 (PPh 3 ) 3 ) is also suitable as a catalyst.

[0094] Among the above, the copper catalyst is inexpensive and preferable. In order to increase the catalytic activity and productivity, it is more preferable to use a polydentate amine in combination with a copper catalyst.

[0095] (c. Polydentate amines) Examples of polydentate amines that can be used as ligands include the following: Bidentate and polydentate amines: 2,2-bipyridine, 4,4'-di-(5-nonyl)-2,2'-bipyridine, N-(n-propyl)pyridylmethanimine, N-(n-octyl)pyridylmethanimine Tridentate and polydentate amines: N,N,N',N'',N''-pentamethyldiethylenetriamine, N-propyl-N,N-di(2-pyridylmethyl)amine Tetradentate polydentate amines: Hexamethyltris(2-aminoethyl)amine (Me 6 TREN), N,N-bis(2-dimethylaminoethyl)-N,N'-dimethylethylenediamine, 2,5,9,12-tetramethyl-2,5,9,12-tetraazatetradecane, 2,6,9,13-tetramethyl-2,6,9,13-tetraazatetradecane, 4,11-dimethyl-1,4,8,11-tetraazabicyclohexadecane, N',N''-dimethyl-N',N''-bis((pyridin-2-yl)methyl)ethane-1,2-diamine, tris[(2-pyridyl)methyl]amine, 2,5,8,12-tetramethyl-2,5,8,12-tetraazatetradecane Pentadentate polydentate amines: N,N,N',N'',N''',N'''',N''''-heptamethyltetraethylenetetramine Hexadentate polydentate amine: N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine · Polyamine: Polyethylenimine.

[0096] (d. Base) A base may be added to the polymerization system to neutralize the acid present or generated in the polymerization system and prevent the accumulation of the acid. Examples of bases include: Monoamines: Monoamines are compounds that have one base moiety per molecule. Examples of monoamines include primary amines (methylamine, aniline, lysine, etc.), secondary amines (dimethylamine, piperidine, etc.), tertiary amines (trimethylamine, triethylamine, etc.), aromatic amines (pyridine, pyrrole, etc.), and ammonia. · Polyamines: Examples of polyamines include diamines (ethylenediamine, tetramethylethylenediamine, etc.), triamines (diethylenetriamine, pentamethyldiethylenetriamine, etc.), tetramines (triethylenetetramine, hexamethyltriethylenetetramine, hexamethylenetetramine, etc.), polyethyleneimines, etc. Inorganic Bases: Inorganic bases are elements or compounds of groups 1 and 2 of the periodic table. Examples of elements of groups 1 and 2 of the periodic table include lithium, sodium, and calcium. Examples of compounds of elements of groups 1 and 2 of the periodic table include sodium methoxide, potassium ethoxide, methyllithium, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium bicarbonate, ammonium bicarbonate, trisodium phosphate, disodium hydrogen phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, sodium acetate, potassium acetate, sodium oxalate, potassium oxalate, sodium phenoxy, potassium phenoxy, sodium ascorbate, and potassium ascorbate.

[0097] (e. Reducing Agent) In living radical polymerization using a copper complex as a catalyst, it is known that polymerization activity is improved by using a reducing agent in combination (ARGET ATRP). In ARGET ATRP, it is believed that polymerization activity is improved by reducing and reducing highly oxidized transition metal complexes (produced by coupling between radicals, etc.) that cause the delay or stop of the polymerization reaction. This allows the transition metal catalyst, which is usually required in the range of hundreds to thousands of ppm, to be reduced to tens to hundreds of ppm. In the production method according to one embodiment of the present invention, a reducing agent is used to achieve the same reaction mechanism as ARGET ATRP. Examples of reducing agents include the following.

[0098] (A reducing agent that does not generate acid when reducing copper complexes) Metals: Examples of metals include alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (beryllium, magnesium, calcium, barium, etc.), main group metals (aluminum, zinc, etc.), and transition metals (copper, nickel, ruthenium, iron, etc.). These metals can also be used in the form of alloys (amalgams) with mercury. Metal compounds: Examples of metal compounds include metal salts and metal complexes. Examples of ligands coordinated to metal complexes include carbon monoxide, olefins, nitrogen-containing compounds, oxygen-containing compounds, phosphorus-containing compounds, and sulfur-containing compounds. More specific examples include compounds of metals and ammonia / amines, titanium trichloride, titanium alkoxides, chromium chloride, chromium sulfate, chromium acetate, iron chloride, copper chloride, copper bromide, tin chloride, zinc acetate, zinc hydroxide, and carbonyl complexes (Ni(CO) 4 , Co 2 CO 8 etc.), olefin complexes ([Ni(cod) 2 ], [RuCl 2 (cod)], [PtCl 2 (cod)]; cod stands for cyclooctadiene), phosphine complexes ([RhCl(P(C 6 H 5 ) 3 ) 3 ], [RuCl 2 (P(C6 H 5 ) 3 ) 2 ], [PtCl 2 (P(C 6 H 5 ) 3 ) 2 ] etc. ·Organotin compounds: Specific examples include tin octoate, tin 2-ethylhexylate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, and dioctyltin thiocarboxylate. Phosphorus or phosphorus compounds: Specific examples include phosphorus, trimethylphosphine, triethylphosphine, triphenylphosphine, trimethylphosphite, triethylphosphite, triphenylphosphite, hexamethylphosphorastriamid, and hexaethylphosphorastriamid. Sulfur or sulfur compounds: Examples include sulfur, Rongalites, hydrosulfites, and thiourea dioxide. Rongalite is a formaldehyde derivative of sulfoxylate, and has the general formula: MSO 2 ·CH 2 O (wherein M is Na or Zn). Specific examples of Rongalite include sodium formaldehyde sulfoxylate and zinc formaldehyde sulfoxylate. Hydrosulfite refers to sodium hyposulfite and its formaldehyde derivatives.

[0099] (Reducing agent that generates acid when reducing copper complex (hydride reducing agent)) Metal hydrides: Specific examples include sodium hydride, germanium hydride, tungsten hydride, aluminum hydrides (diisobutylaluminum hydride, lithium aluminum hydride, sodium aluminum hydride, sodium triethoxyaluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride, etc.), organotin hydrides (triphenyltin hydride, tri-n-butyltin hydride, diphenyltin hydride, di-n-butyltin hydride, triethyltin hydride, trimethyltin hydride, etc.). Silicon hydrides: Specific examples include trichlorosilane, trimethylsilane, triethylsilane, diphenylsilane, phenylsilane, and polymethylhydrosiloxane. Boron hydrides, such as borane, diborane, sodium borohydride, sodium trimethoxyborohydride, sodium borohydride sulfide, sodium cyanide borohydride, lithium cyanide borohydride, lithium borohydride, lithium triethylborohydride, lithium tri-s-butylborohydride, lithium tri-t-butylborohydride, calcium borohydride, potassium borohydride, zinc borohydride, and tetra-n-butylammonium borohydride. Nitrogen-hydrogen compounds: Examples include hydrazine and diimide. Phosphorus or phosphorus compounds: Specific examples include phosphines and diazaphospholenes. · Sulfur or sulfur compounds: A specific example is hydrogen sulfide. Organic compounds that exhibit reducing properties: Examples include alcohols, aldehydes, phenols, and organic acid compounds. Examples of alcohols include methanol, ethanol, propanol, and isopropanol. Examples of aldehydes include formaldehyde, acetaldehyde, benzaldehyde, and formic acid. Examples of phenols include phenol, hydroquinone, dibutylhydroxytoluene, and tocopherol. Examples of organic acid compounds include citric acid, oxalic acid, ascorbic acid, ascorbate, and ascorbate esters.

[0100] The reducing agent may also be generated in the polymerization system by electrolytic reduction. In electrolytic reduction, electrons generated at the cathode directly (or after solvation) exert a reducing effect. In other words, the reducing agent may be generated by electrolysis.

[0101] (f. Solvent) Examples of solvents include the following: However, ATRP can also be carried out in the absence of a solvent. Highly polar aprotic solvents: dimethylsulfoxide (DMSO), dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidone Carbonate solvents: ethylene carbonate, propylene carbonate Alcohol-based solvents: methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol Nitrile solvents: acetonitrile, propionitrile, benzonitrile Ketone solvents: acetone, methyl ethyl ketone, methyl isobutyl ketone Ether solvents: diethyl ether, tetrahydrofuran Halogenated carbon solvents: methylene chloride, chloroform Ester solvents: ethyl acetate, butyl acetate Hydrocarbon solvents: pentane, hexane, heptane, cyclohexane, octane, decane, benzene, toluene, xylene ·Other solvents: ionic liquids, water, supercritical fluids.

[0102] In the ATRP (ARGET) system using a reducing agent, it is preferable that the transition metal or transition metal compound, polydentate amine, base, reducing agent, monomer and initiator are uniform in the polymerization system from the viewpoints of reaction control, polymerization reaction rate, ease of charging and risk of scale-up. Therefore, it is preferable to select a solvent that can dissolve these substances.

[0103] [A2. (Meth)acrylic polymer (B)] The (meth)acrylic polymer (B) has an average of 1.0 or more (meth)acryloyl groups per molecule at the molecular terminals. In one embodiment, the (meth)acryloyl group has a structure represented by the following general formula (5). -OC(O)C(R 5 )=CH 2 (5).

[0104] In general formula (5), R 5 R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group may be optionally substituted with one or more heteroatoms selected from the group consisting of oxygen atoms, nitrogen atoms, sulfur atoms, fluorine atoms, chlorine atoms, bromine atoms and iodine atoms. 5 Specific examples of 3 , C.H. 2 CH 3 , (CH 2 ) n CH 3 (n is an integer from 2 to 19), C 6 H 5 , C.H. 2 From the viewpoint of reactivity of the (meth)acrylic polymer (B), R 5 is H or CH 3 is preferred.

[0105] The number of (meth)acryloyl groups possessed by the (meth)acrylic polymer (B) is, on average, 1.0 or more, preferably 1.2 or more, more preferably 1.4 or more per molecule. The upper limit of the number of (meth)acryloyl groups possessed by the (meth)acrylic polymer (B) can be 2. If the number of (meth)acryloyl groups is within the above range, the (meth)acrylic polymers (B) are sufficiently crosslinked with each other by light irradiation, and a cured product having sufficient strength can be obtained.

[0106] Examples of the (meth)acrylic acid ester monomer that is the raw material of the main chain of the (meth)acrylic polymer (B) include the (meth)acrylic acid ester monomers (α) to (δ) and specific monomers listed in Section [A1.1.]. The monomer that is the raw material of the (meth)acrylic polymer (B) is preferably an acrylic acid ester monomer, more preferably n-butyl acrylate. When such a (meth)acrylic polymer (B) is used, a curable composition that has low viscosity and good workability can be obtained.

[0107] The (meth)acrylic polymer (B) may have repeating units derived from two or more kinds of (meth)acrylic acid ester monomers. The repeating units derived from the (meth)acrylic acid ester monomers contained in the (meth)acrylic polymer (B) are preferably 70% by weight or more, more preferably 90% by weight or more, based on all the repeating units contained in the polymer (B). When the (meth)acrylic polymer (B) having a content of repeating units derived from the (meth)acrylic acid ester monomers of 70% or more is used, a cured product having good mechanical properties and durability can be obtained.

[0108] The number average molecular weight of the (meth)acrylic polymer (B) is preferably 500 to 1,000,000, more preferably 3,000 to 100,000, further preferably 5,000 to 80,000, and particularly preferably 8,000 to 50,000. If the molecular weight is too low, the inherent properties of the (meth)acrylic polymer tend to be difficult to exhibit. If the molecular weight is too high, handling tends to be difficult.

[0109] The molecular weight distribution of the (meth)acrylic polymer (B) is preferably 1.8 or less, and more preferably 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, and 1.3 or less in that order. If the molecular weight distribution is within the above range, a curable composition having low viscosity and good workability can be obtained.

[0110] The weight average molecular weight and number average molecular weight can be measured, for example, by gel permeation chromatography (GPC). For GPC measurement, chloroform can be used as the mobile phase and a polystyrene gel column can be used as the stationary phase. These molecular weights can be calculated in terms of polystyrene.

[0111] [A2.1. Method for producing (meth)acrylic polymer (B)] The (meth)acrylic polymer (B) can be obtained by various polymerization methods. Radical polymerization is preferred, and controlled radical polymerization is more preferred, since various monomers can be used and control is easy. Among controlled radical polymerizations, living radical polymerization is preferred, since the molecular weight and molecular weight distribution of the obtained (meth)acrylic polymer (B) can be easily controlled. Among living radical polymerizations, atom transfer radical polymerization is preferred, since it is easy to introduce a (meth)acryloyl group to the polymer terminal.

[0112] A preferred embodiment of the method for producing the (meth)acrylic polymer (B) will be described below. The descriptions in (General matters regarding living radical polymerization) and (b. Polymerization solvent) to (f. Solvent) in Section [A1.4.] are also applicable to the preferred embodiment of the method for producing the (meth)acrylic polymer (B), so these descriptions are incorporated herein by reference and will not be repeated. In addition, the descriptions in JP-A-2005-232419, JP-A-2006-291073, etc. can be referenced.

[0113] (Initiator) In order to obtain a (meth)acrylic polymer (B) having (meth)acryloyl groups at both ends of the molecule, it is preferable to use an organic halide or a halogenated sulfonyl compound having two or more initiation points as an initiator. Specific examples include compounds represented by the following formulas.

[0114] [ka] TIFF0007674852000002.tif201162

[0115] (Method of Introducing a (Meth)acryloyl Group) A known method can be used to introduce a (meth)acryloyl group into a (meth)acrylic polymer. A method of substituting a terminal halogen group of a (meth)acrylic polymer having a structure of the following formula (A) with a compound having a (meth)acryloyl group of the following formula (B) is preferred because it is easier to control. -CR 6 R 7 X (A) M + -OC(O)C(R 5 )=CH 2 (B).

[0116] In formula (A), R 6 and R 7 is a group bonded to the ethylenically unsaturated group of the (meth)acrylic acid ester monomer. X represents a chlorine atom, a bromine atom, or an iodine atom. In formula (B), R 5 is defined the same as in general formula (5). + represents an alkali metal or quaternary ammonium ion.

[0117] The (meth)acrylic polymer having a terminal structure represented by formula (A) can be produced by a method of polymerizing a (meth)acrylic monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst. Alternatively, the (meth)acrylic polymer having a terminal structure represented by formula (A) can also be produced by a method of polymerizing a (meth)acrylic monomer using a halogen compound as a chain transfer agent. The former production method is preferred.

[0118] Alkali metal ion M + Specific examples of the quaternary ammonium ion M include lithium ion, sodium ion, and potassium ion. +Specific examples of M include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, and dimethylpiperidinium ion. + are sodium ions and potassium ions.

[0119] The amount of the compound of formula (B) is preferably 1 to 5 equivalents, more preferably 1.0 to 1.2 equivalents, relative to the halogen group of formula (A). The above reaction is a nucleophilic substitution reaction, and is therefore preferably carried out in a polar solvent. Examples of polar solvents include tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric triamide, and acetonitrile. The reaction temperature of the above reaction is preferably 0 to 150°C, more preferably 20 to 100°C, from the viewpoint of maintaining the polymerizability of the (meth)acryloyl group.

[0120] [A3. Photoradical polymerization initiator (C)] The curable composition according to one embodiment of the present invention contains a photoradical polymerization initiator (C). The curable composition contains a (meth)acrylic polymer (B) having a (meth)acryloyl group and the photoradical polymerization initiator (C), and is therefore cured by light irradiation (UV irradiation or the like).

[0121] Examples of the photoradical polymerization initiator (C) include acetophenone, propiophenone, benzophenone, xanthol, fluorene, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, and 3-chloroxantho. benzoin, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoyl, benzoin methyl ether, benzoin butyl ether, bis(4-dimethylaminophenyl)ketone, benzyl methoxyketal, 2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1.

[0122] Further examples of the photoradical polymerization initiator (C) include acylphosphine oxide-based photopolymerization initiators. Acylphosphine oxide-based photopolymerization initiators are preferred because they have excellent deep curing properties when irradiated with UV light. Specific examples of acylphosphine oxide-based photopolymerization initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, bis(2,6-dimethylbenzoyl)-phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-isobutylphosphine oxide, bis(2,6-dimethoxybenzoyl)-isobutylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-phenylphosphine oxide. Among these, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide are preferred.

[0123] Among the above-mentioned photoradical polymerization initiators (C), 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide are preferred due to their high reactivity. In one embodiment, the curable composition contains both an acylphosphine oxide and a phenyl ketone compound.

[0124] [A4. Condensation catalyst (D)] The curable composition according to one embodiment of the present invention contains a condensation catalyst (D). The curable composition contains a (meth)acrylic polymer (A) having a trialkoxysilyl group and a condensation catalyst (D), and thus reacts with moisture to cure.

[0125] Examples of such condensation catalysts (D) include tin-based curing catalysts, other metal compounds, amines, and phosphate esters.

[0126] Specific examples of tin-based curing catalysts include dialkyltin carboxylates (dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethyl maleate, dibutyltin diethyl maleate, dibutyltin dibutyl maleate, dibutyltin diisooctyl maleate, dibutyltin ditridecyl maleate, dibutyltin dibenzyl maleate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethyl maleate, dioctyltin diisooctyl maleate, etc.); dialkyltin oxides (dibutyltin oxide, dioctyltin oxide, a mixture of dibutyltin oxide and phthalic acid ester, etc.); tetravalent tin compounds (dialkyltin oxide, dialkyltin diacetate, etc.) and low molecular weight compounds having an alkoxysilyl group. Examples of such compounds include reaction products with silicon compounds (such as tetraethoxysilane, methyltriethoxysilane, diphenyldimethoxysilane, and phenyltrimethoxysilane); divalent tin compounds (such as tin octoate, tin naphthenate, and tin stearate); monoalkyltin compounds (such as monobutyltin compounds (such as monobutyltin trisoctoate and monobutyltin triisopropoxide), and monooctyltin compounds); reaction products or mixtures of amine compounds and organic tin compounds (such as reaction products or mixtures of laurylamine and tin octoate); chelate compounds (such as dibutyltin bisacetylacetonate, dioctyltin bisacetylcetonate, dibutyltin bisethylacetonate, and dioctyltin bisethylacetonate); and tin alcoholates (such as dibutyltin dimethylate, dibutyltin diethylate, dioctyltin dimethylate, and dioctyltin diethylate).

[0127] Examples of other metal compounds include titanate esters (tetrabutyl titanate, tetrapropyl titanate, tetra(2-ethylhexyl) titanate, isopropoxytitanium bis(ethylacetoacetate), etc.); organoaluminum compounds (aluminum trisacetylacetonate, aluminum trisethylacetoacetate, di-isopropoxyaluminum ethylacetoacetate, etc.); and metal salts of carboxylic acids (2-ethylhexanoic acid, neodecanoic acid, versatic acid, oleic acid, naphthenic acid, etc.). For example, bismuth carboxylate, iron carboxylate, titanium carboxylate, lead carboxylate, vanadium carboxylate, zirconium carboxylate, calcium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate, cerium carboxylate, nickel carboxylate, cobalt carboxylate, zinc carboxylate, aluminum carboxylate; reaction products or mixtures of metal salts of carboxylate with amine compounds (such as laurylamine); chelate compounds (such as zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, dibutoxyzirconium diacetylacetonate, zirconium acetylacetonate bis(ethylacetoacetate), titanium tetraacetylacetonate, etc.);

[0128] Examples of amines include aliphatic primary amines (methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, cyclohexylamine, etc.); aliphatic secondary amines (dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dioctylamine, di(2-ethylhexyl)amine, didecylamine, dilaurylamine, dicetylamine, distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine, etc.); aliphatic tertiary amines (triamylamine, trihexylamine, trioctylamine, etc.); aliphatic unsaturated amines (triallylamine, oleylamine, etc.); aromatic amines (laurylaniline, stearylaniline, etc.). phosphorus, triphenylamine, etc.); other amines (monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo(5,4,0)undecene-7 (DBU), etc.); salts of amine compounds (such as carboxylates); reaction products or mixtures of amine compounds and organotin compounds (such as reaction products or mixtures of laurylamine and tin octylate); low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products of excess polyamines and epoxy compounds.

[0129] Examples of phosphate esters include (CH 3 O) 2 -P(=O)(-OH), (CH 3 O)-P(=O)(-OH) 2 , (C 2 H 5 O)2 -P(=O)(-OH)、(C 2 H 5 O)-P(=O)(-OH) 2 、(C 3 H 7 O) 2 -P(=O)(-OH)、(C 3 H 7 O)-P(=O)(-OH) 2 、(C 4 H 9 O) 2 -P(=O)(-OH)、(C 4 H 9 O)-P(=O)(-OH) 2 、(C 8 H 17 O) 2 -P(=O)(-OH)、(C 8 H 17 O)-P(=O)(-OH) 2 、(C 10 H 21 O) 2 -P(=O)(-OH)、(C 10 H 21 O)-P(=O)(-OH) 2 、(C 13 H 27 O) 2 -P(=O)(-OH)、(C 13 H 27 O)-P(=O)(-OH) 2 、(C 16 H 33 O) 2 -P(=O)(-OH)、(C 16 H 33 O)-P(=O)(-OH) 2 、(HO-C 6 H 12 O) 2 -P(=O)(-OH)、(HO-C 6 H 12 O)-P(=O)(-OH) 2 、(HO-C 8 H 16 O)-P(=O)(-OH)、(HO-C 8 H 16 O)-P(=O)(-OH) 2 、[(CH 2OH)(CHOH)O] 2 -P(=O)(-OH), [(CH 2 OH)(CHOH)O]-P(=O)(-OH) 2 , [(CH 2 OH)(CHOH)C 2 H 4 O] 2 -P(=O)(-OH), [(CH 2 OH)(CHOH)C 2 H 4 O]-P(=O)(-OH) 2 Examples include:

[0130] Among these, amines and phosphate esters are preferred from the viewpoint of the storage stability of the curable composition.

[0131] [A5. (Meth)acrylic monomers (E)] The curable composition according to one embodiment of the present invention may contain a (meth)acrylic monomer (E). The (meth)acrylic monomer (E) has the function of adjusting the viscosity of the curable composition and improving the mechanical properties of the cured product. Therefore, the curable composition containing the (meth)acrylic monomer (E) is easy to handle and has excellent mechanical properties of the cured product.

[0132] The (meth)acrylic monomer preferably has a molecular weight of less than 500. Specific examples of the (meth)acrylic monomer (E) include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, tricyclodecanyl (meth)acrylate, vinyl acetate, acrylonitrile, acrylamide, styrene, itaconic acid, maleic anhydride, methylol acrylamide, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl ... Examples of suitable acrylates include hydroxypropyl, 4-hydroxybutyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, ethyl carbitol (meth)acrylate, tricyclodecanyloxyethyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxyethyl (meth)acrylate, 2-phenoxydiethylene glycol, isobornyl (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, methoxypropylene (meth)acrylate, and tetrahydrofuryl (meth)acrylate.

[0133] Further specific examples of the (meth)acrylic monomer (E) include compounds represented by the following formula:

[0134] [ka] TIFF0007674852000004.tif156162TIFF0007674852000005.tif164164TIFF0007674852000006.tif207163

[0135] [A6. Silane coupling agent (F)] The curable composition according to one embodiment of the present invention may contain a silane coupling agent (F). The silane coupling agent (F) functions as an adhesion promoter. Therefore, by including the silane coupling agent (F) in the curable composition, the adhesion of the cured product can be improved.

[0136] Specific examples of the silane coupling agent (F) include isocyanate group-containing silanes (γ-isocyanate propyl trimethoxy silane, γ-isocyanate propyl triethoxy silane, γ-isocyanate propyl methyl diethoxy silane, γ-isocyanate propyl methyl dimethoxy silane, etc.); amino group-containing silanes (γ-aminopropyl trimethoxy silane, γ-aminopropyl triethoxy silane, γ-aminopropyl methyl dimethoxy silane, γ-aminopropyl methyl diethoxy silane, N-(β-aminoethyl)-γ-aminopropyl Trimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, etc.; mercapto group-containing silanes (γ-mercaptopropyltrimethoxysilane, γ -Mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, etc.; epoxy group-containing silanes (γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, etc.); carboxysilanes (β-carboxyethyltriethoxysilane, β-carboxyethyltriethoxysilane, carboxyethylphenylbis(2-methoxyethoxy)silane, N-(β-carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane, etc.); vinyl-type unsaturated group-containing silanes (vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acroyloxypropylmethyltriethoxysilane, etc.); halogen-containing silanes (γ-chloropropyltrimethoxysilane, etc.); isocyanurate silanes (tris(trimethoxysilyl)isocyanurate, etc.).In addition, derivatives obtained by modifying silane coupling agents, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, and silylated polyesters, can also be used as silane coupling agents.

[0137] [A7. Other ingredients] The curable composition according to one embodiment of the present invention may contain the following components in addition to the above-mentioned components.

[0138] [A7.1. Filler] Examples of the filler include the fillers described in JP-A-2005-232419, paragraph 0158. Among these fillers, crystalline silica, fused silica, dolomite, carbon black, calcium carbonate, titanium oxide and talc are preferred.

[0139] In order to obtain a hardened product with high strength, it is preferable to use, as the filler, one or more types selected from the group consisting of crystalline silica, fused silica, silicic anhydride, hydrated silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and active zinc oxide. In particular, ultrafine powdered silica is preferable, and the specific surface area (BET adsorption method) of the silica is 50 m or less. 2 / g or more is preferable, and 50 to 400m 2 / g is more preferable, and 100 to 300m 2 Silica whose surface has been hydrophobically treated with an organosilicon compound (such as organosilane, organosilazane, or diorganopolysiloxane) is also preferred.

[0140] On the other hand, in order to obtain a cured product with good extensibility by suppressing the strength of the cured product, it is preferable to use one or more types selected from the group consisting of titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide and shirasuballoon.

[0141] The larger the specific surface area of ​​calcium carbonate, the greater the effect of improving the breaking strength and breaking elongation of the cured product. For the purpose of improving the thixotropy of the curable composition and the breaking strength and breaking elongation of the cured product, it is preferable to use colloidal calcium carbonate. On the other hand, for the purpose of increasing the amount of the curable composition and reducing costs, it is preferable to use heavy calcium carbonate.

[0142] Calcium carbonate that has been subjected to a surface treatment is more preferably used. When surface-treated calcium carbonate is used, the workability of the curable composition is improved and the storage stability effect is enhanced. Examples of surface treatment agents for calcium carbonate include those described in paragraph 0161 of JP-A-2005-232419. The amount of the surface treatment agent is preferably 0.1 to 20% by weight, more preferably 1 to 5% by weight, based on the total weight of calcium carbonate. If the amount is 0.1% by weight or more, the effect of improving the workability can be sufficiently obtained. If the amount is 20% by weight or less, the storage stability of the curable composition can be maintained without deterioration.

[0143] The filler may be used alone or in combination of two or more. The amount of the filler is preferably 5 to 1000 parts by weight, more preferably 20 to 500 parts by weight, and even more preferably 40 to 300 parts by weight, based on 100 parts by weight of the total of the (meth)acrylic polymer (A) and the (meth)acrylic polymer (B). When the amount is 5 parts by weight or more, the effect of improving the breaking strength, breaking elongation, adhesiveness, and weather-resistant adhesiveness of the cured product can be sufficiently obtained. When the amount is 1000 parts by weight or less, the workability of the curable composition is not deteriorated.

[0144] [A7.1.1. Microscopic hollow particles] The curable composition may contain hollow microparticles in addition to the filler.

[0145] Examples of micro hollow particles include hollow bodies made of inorganic or organic materials having a diameter of 1 mm or less, preferably 500 μm or less, and more preferably 200 μm or less. 3The preferred microhollow bodies are 0.5 g / cm or less. 3 More preferred are hollow microparticles having the following structure: By blending hollow microparticles, the cured product can be made lighter in weight and costs can be reduced without impairing the flexibility and mechanical strength of the cured product.

[0146] Examples of inorganic hollow microparticles include those described in paragraphs 0168-0170 of JP 2005-232419 A. In order to improve the dispersibility and workability of the curable composition, hollow microparticles whose surfaces have been treated with a surface treatment agent may be used. Examples of the surface treatment agent include fatty acids, fatty acid esters, rosin, rosin acid lignin, silane coupling agents, titanium coupling agents, aluminum coupling agents, and polypropylene glycol.

[0147] The hollow microparticles may be used alone or in combination of two or more kinds. The amount of hollow microparticles is preferably 0.1 to 50 parts by weight, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the total of the (meth)acrylic polymer (A) and the (meth)acrylic polymer (B). If the amount is 0.1 part by weight or more, the effect of weight reduction can be sufficiently obtained. If the amount is 50 parts by weight or less, the physical properties of the cured product can be sufficiently maintained. For hollow microparticles having a specific gravity of 0.1 or more, the amount is preferably 3 to 50 parts by weight, more preferably 5 to 30 parts by weight.

[0148] [A7.2. Antioxidants] Examples of the antioxidant include p-phenylenediamine antioxidants, amine antioxidants, and hindered phenol antioxidants. Secondary antioxidants (phosphorus antioxidants, sulfur antioxidants, etc.) are also included in the antioxidant.

[0149] The antioxidant may be used alone or in combination of two or more kinds. The amount of the antioxidant is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight in total of the (meth)acrylic polymer (A) and the (meth)acrylic polymer (B).

[0150] [A7.3. Plasticizers] Examples of the plasticizer include those described in JP-A-2005-232419, paragraph 0173. Among these, polyester plasticizers and vinyl polymers are preferred because they have a significant viscosity reducing effect and a low volatilization rate during a heat resistance test.

[0151] It is also preferable to add a polymer plasticizer. Compared with low molecular weight plasticizers, polymer plasticizers can maintain their initial physical properties for a long period of time. The number average molecular weight of the polymer plasticizer is preferably 500 to 15,000, more preferably 800 to 10,000, and even more preferably 1,000 to 8,000. If the number average molecular weight is 500 or more, the outflow of the plasticizer due to heating or contact with a liquid can be prevented. If the number average molecular weight is 15,000 or less, the increase in viscosity can be suppressed and workability can be ensured.

[0152] The molecular weight distribution of the polymer plasticizer is preferably less than 1.8, and more preferably 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, and 1.3 or less in that order.

[0153] From the viewpoints of compatibility with the (meth)acrylic polymer (A) and the (meth)acrylic polymer (B), weather resistance, and heat aging resistance, vinyl polymers are preferred as polymer plasticizers. Among vinyl polymers, (meth)acrylic polymers are preferred, and acrylic polymers are more preferred. Acrylic polymers can be produced by solution polymerization or solvent-free synthesis methods. Acrylic plasticizers produced by solvent-free synthesis methods are produced by high-temperature continuous polymerization without using solvents and chain transfer agents (see U.S. Pat. No. 4,414,370, JP-A-59-6207, JP-B-5-58005, JP-A-1-313522, U.S. Pat. No. 5,010,166, etc.). Specific examples of acrylic plasticizers produced by solvent-free synthesis methods include the Toagosei UP series.

[0154] Other preferred acrylic polymers include polymers obtained by living radical polymerization. Acrylic polymers obtained by living radical polymerization (particularly preferably atom transfer radical polymerization) are preferred in that they have a narrow molecular weight distribution and a low viscosity.

[0155] The plasticizer may be used alone or in combination of two or more kinds. In one embodiment, both a polymer plasticizer and a low molecular weight plasticizer may be blended. A plasticizer may be blended during the production of the (meth)acrylic polymer (A) and / or the (meth)acrylic polymer (B).

[0156] The amount of the plasticizer is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the total of the (meth)acrylic polymer (A) and the (meth)acrylic polymer (B). If the amount is 1 part by weight or more, the effect of the plasticizer is sufficiently exhibited. If the amount is 100 parts by weight or less, the mechanical strength of the cured product is not reduced.

[0157] [A7.3.1. Reactive diluents] In addition to the plasticizer, the curable composition may also contain a reactive diluent.

[0158] As the reactive diluent, an organic compound having a boiling point of 100°C or more at normal pressure is particularly preferred. Such an organic compound does not volatilize when the curable composition is cured, so that it is possible to suppress the change in shape before and after curing and the adverse effects on the environment. Specific examples of the reactive diluent include 1-octene, 4-vinylcyclohexene, allyl acetate, 1,1-diacetoxy-2-propene, methyl 1-undecenoate, and 8-acetoxy-1,6-octadiene.

[0159] The reactive diluent may be used alone or in combination of two or more kinds. The amount of the reactive diluent is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 70 parts by weight, and further preferably 1 to 50 parts by weight, based on 100 parts by weight in total of the (meth)acrylic polymer (A) and the (meth)acrylic polymer (B).

[0160] [A7.4. Light stabilizers] Examples of light stabilizers include those described in Kenichi Saruwatari et al., Antioxidant Handbook, Taiseisha, 1976; Zenjiro Osawa (ed.), Deterioration and Stabilization of Polymer Materials, CMC, 1990, pp. 235-242.

[0161] A preferred light stabilizer is an ultraviolet absorber. Specific examples of ultraviolet absorbers include benzotriazole-based compounds (Tinuvin P, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 329, Tinuvin 213, etc.); triazine-based compounds (Tinuvin 1577, etc.); benzophenone-based compounds (CHIMASSORB81, etc.); and benzoate-based compounds (Tinuvin 120, etc.). Another preferred light stabilizer is a hindered amine-based compound. Examples of hindered amine compounds include the compounds described in JP-A-2006-274084. A combination of an ultraviolet absorber and a hindered amine-based compound is also preferred because it may produce a synergistic effect.

[0162] The embodiment of combining the light stabilizer and the above-mentioned antioxidant is preferable because it has a synergistic effect, particularly improving weather resistance. Products containing both a light stabilizer and an antioxidant (Tinuvin C353, Tinuvin B75, etc.) may be added.

[0163] The amount of the light stabilizer is preferably 0.1 to 10 parts by weight per 100 parts by weight of the total of the (meth)acrylic polymer (A) and the (meth)acrylic polymer (B). If the amount is 0.1 part by weight or more, an improvement effect in weather resistance can be obtained. Even if the amount exceeds 10 parts by weight, there is not much difference in the effect obtained, so 10 parts by weight or less is economically preferable.

[0164] [A7.5. Adhesion promoters] Examples of adhesion promoters include vinyl monomers having a polar group, and preferably vinyl monomers containing an acidic group. More specific examples of substances are described in paragraph 0184 of JP-A-2005-232419.

[0165] Examples of polar group-containing vinyl monomers include carboxy group-containing monomers and their esters, sulfonic acid group-containing monomers, and phosphoric acid group-containing monomers. Specific examples of carboxy group-containing monomers include (meth)acrylic acid, acryloxypropionic acid, citraconic acid, fumaric acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, and their derivatives. Specific examples of esters of carboxy group-containing monomers include maleic acid esters, 2-(meth)acryloyloxyethyl succinic acid, and 2-(meth)acryloyloxyethyl hexahydrophthalic acid. Specific examples of sulfonic acid group-containing monomers include vinyl sulfonic acid, (meth)acrylic sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, vinyl benzene sulfonic acid, 2-acrylamido-2-methyl propane sulfones, and salts thereof. Specific examples of the phosphate group-containing monomer include 2-((meth)acryloyl diethyl phosphate), 2-(meth)acryloyloxypropyl phosphate, 2-(meth)acryloyloxy-3-chloropropyl phosphate, and 2-(meth)acryloyloxyethyl phenyl phosphate. Among these, the phosphate group-containing monomer is preferred. In addition, these monomers may have two or more polymerizable groups.

[0166] Examples of adhesion promoters other than polar group-containing vinyl monomers include epoxy resins, phenolic resins, modified phenolic resins, cyclopentadiene-phenolic resins, xylene resins, coumarone resins, petroleum resins, terpene resins, terpene phenolic resins, rosin ester resins, sulfur, alkyl titanates, and aromatic polyisocyanates.

[0167] The adhesion promoter may be used alone or in combination of two or more. The amount of the adhesion promoter is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total of the (meth)acrylic polymer (A) and the (meth)acrylic polymer (B). When the amount is 0.01 part by weight or more, the effect of improving adhesion can be sufficiently obtained. When the amount is 20 parts by weight or less, the physical properties of the cured product are not likely to deteriorate.

[0168] [A7.6. Solvents] Examples of the solvent include aromatic hydrocarbon solvents (toluene, xylene, etc.), ester solvents (ethyl acetate, butyl acetate, amyl acetate, cellosolve acetate, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, etc.). These solvents may be those used in the production of the (meth)acrylic polymer (A) and / or the (meth)acrylic polymer (B).

[0169] [A7.7. Other additives] Examples of other additives include flame retardants, antiaging agents, radical inhibitors, metal deactivators, antiozonants, phosphorus-based peroxide decomposers, lubricants, pigments, and foaming agents. Only one type of other additives may be used, or two or more types may be used in combination. Specific examples of such additives are described in, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, and JP-A-64-22904.

[0170] [A8. Composition of the curable composition] In the curable composition according to one embodiment of the present invention, when the amount of the (meth)acrylic polymer (A) is 100 parts by weight, the lower limit of the amount of the (meth)acrylic polymer (B) is preferably 50 parts by weight or more, more preferably 100 parts by weight or more, and even more preferably 125 parts by weight or more. When the amount of the (meth)acrylic polymer (A) is 100 parts by weight, the upper limit of the amount of the (meth)acrylic polymer (B) is preferably 250 parts by weight or less, more preferably 200 parts by weight or less, and even more preferably 175 parts by weight or less. When the blending ratio of the (meth)acrylic polymer (A) and the (meth)acrylic polymer (B) is within the above range, the mechanical properties of the cured product obtained from the curable composition are excellent.

[0171] In the curable composition according to one embodiment of the present invention, when the amount of the (meth)acrylic polymer (B) is 100 parts by weight, the lower limit of the amount of the photoradical polymerization initiator (C) is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, and even more preferably 1.0 parts by weight or more. When the amount of the (meth)acrylic polymer (B) is 100 parts by weight, the upper limit of the amount of the photoradical polymerization initiator (C) is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and even more preferably 10 parts by weight or less. When the amount of the photoradical polymerization initiator (C) is within the above range, a curable composition having excellent curability can be obtained.

[0172] In the curable composition according to one embodiment of the present invention, when the amount of the (meth)acrylic polymer (A) is 100 parts by weight, the lower limit of the amount of the condensation catalyst (D) is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, and even more preferably 1.0 parts by weight or more. When the amount of the (meth)acrylic polymer (A) is 100 parts by weight, the upper limit of the amount of the condensation catalyst (D) is preferably 15 parts by weight or less, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less. When the amount of the condensation catalyst (D) is within the above range, a curable composition having excellent storage stability and curability can be obtained.

[0173] In the curable composition according to one embodiment of the present invention, when the total amount of the (meth)acrylic polymer (A) and the (meth)acrylic polymer (B) is 100 parts by weight, the lower limit of the amount of the (meth)acrylic monomer (E) is preferably 25 parts by weight or more, more preferably 50 parts by weight or more, and even more preferably 75 parts by weight or more. When the total amount of the (meth)acrylic polymer (A) and the (meth)acrylic polymer (B) is 100 parts by weight, the upper limit of the amount of the (meth)acrylic monomer (E) is preferably 200 parts by weight or less, more preferably 175 parts by weight or less, and even more preferably 150 parts by weight or less. When the amount of the (meth)acrylic monomer (E) is within the above range, a curable composition having excellent handling properties can be obtained, and a cured product having excellent mechanical properties can be obtained.

[0174] In the curable composition according to one embodiment of the present invention, when the total amount of the (meth)acrylic polymer (A) and the (meth)acrylic polymer (B) is 100 parts by weight, the lower limit of the amount of the silane coupling agent (F) is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, and even more preferably 1.0 parts by weight or more. When the total amount of the (meth)acrylic polymer (A) and the (meth)acrylic polymer (B) is 100 parts by weight, the upper limit of the amount of the silane coupling agent (F) is preferably 10 parts by weight or less, more preferably 7.5 parts by weight or less, and even more preferably 5.0 parts by weight or less. When the amount of the silane coupling agent (F) is within the above range, the cured product exhibits excellent adhesion.

[0175] ≪B. Cured product≫ The cured product according to one embodiment of the present invention is obtained by curing the curable composition described above. Methods for curing the curable composition include irradiation with light and contact with moisture.

[0176] For curing by light irradiation, light rays and electron beams can be used. Examples of sources of light rays and / or electron beams include high-pressure mercury lamps, low-pressure mercury lamps, electron beam irradiation devices, halogen lamps, light-emitting diodes, semiconductor lasers, and metal halides. The temperature during curing by light irradiation is preferably 0 to 150°C, more preferably 5 to 120°C.

[0177] The relative humidity during curing by contact with moisture is preferably 5 to 95%, more preferably 10 to 80%.

[0178] The cured product according to one embodiment of the present invention can be used, for example, in flat panel displays and conformal coatings.

[0179] [B1. Flat Panel Display] The cured product according to one embodiment of the present invention has improved adhesion to glass, and is therefore suitable for use as a material for filling the gap between a liquid crystal module and a top cover of a flat panel display. The curable composition according to one embodiment of the present invention cures quickly in areas where light can be irradiated, and also cures eventually due to moisture in areas where light cannot be irradiated. Therefore, it can also be used in flat panel displays with high designability.

[0180] Examples of flat panel displays include liquid crystal displays, organic electroluminescence displays, and organic TFT displays. Examples of electronic devices that use flat panel displays include touch panels, mobile phones, computers, car navigation systems, and televisions.

[0181] When the curable composition according to one embodiment of the present invention is applied to a flat panel display, it may be applied by a known method. Examples of the application method include a method using a dispenser, a method using a coater, and a method using a spray. From the viewpoint of preventing dripping during and after application and preventing the inclusion of foreign matter, the method using a dispenser is preferred.

[0182] [B2. Conformal Coating] The curable composition according to one embodiment of the present invention can give a cured product with high strength, elongation and heat cycle resistance, and can therefore be suitably used for conformal coating.

[0183] Conformal coatings can be applied, for example, to printed circuit boards and components mounted on printed circuit boards.

[0184] When the curable composition according to one embodiment of the present invention is applied to a conformal coating, it may be applied by a known method. Examples of application methods include spraying, immersion, syringe application, and brush application. From the viewpoint of productivity, spraying or immersion is preferred.

[0185] 〔summary〕 The present invention includes the following aspects. <1> A (meth)acrylic polymer (A) having an average of 1.0 or more trialkoxysilyl groups per molecule at or near the terminals of the molecule; A (meth)acrylic polymer (B) having an average of 1.0 or more (meth)acryloyl groups per molecule at the molecular terminals; A photoradical polymerization initiator (C); A condensation catalyst (D); A curable composition comprising: <2> The (meth)acrylic polymer (A) is a (meth)acrylic polymer (A1) that satisfies the following conditions: <1> A curable composition according to claim 1, The (meth)acrylic polymer (A1) has an X block and a Y block; The molecule of the (meth)acrylic polymer (A1) contains an XY diblock structure or an XYX triblock structure in the molecule; the number of repeating units derived from a (meth)acrylic acid ester monomer having a trialkoxysilyl group contained in the X block is, on average, 1.0 or more; the repeating unit derived from a (meth)acrylic acid ester monomer having a trialkoxysilyl group contained in the Y block is 0 to 3% by weight based on the weight of all repeating units contained in the Y block; The (meth)acrylic polymer (A1) has a molecular weight distribution (Mw / Mn) of 1.8 or less. <3> The number of trialkoxysilyl groups contained in the (meth)acrylic polymer (A1) is more than 2.0 on average per molecule. <2> The curable composition according to claim 1. <4> The (meth)acrylic polymer (A) has trialkoxysilyl groups near both ends of the molecule. <1> ~ <3> 2. The curable composition according to claim 1 . <5> The (meth)acrylic polymer (B) has a molecular weight distribution (Mw / Mn) of 1.8 or less. <1> ~ <4> The curable composition according to any one of claims 1 to 5. <6> Further containing a (meth)acrylic monomer (E), <1> ~ <5> 2. The curable composition according to claim 1 . <7> Further containing a silane coupling agent (F), <1> ~ <6> 2. The curable composition according to claim 1 . <8> The trialkoxysilyl group is a trimethoxysilyl group. <1> ~ <7> 2. The curable composition according to claim 1 . <9> The (meth)acrylic polymer (A) contains 50% by weight or more of repeating units derived from n-butyl acrylate based on the weight of all repeating units contained in the (meth)acrylic polymer (A). <1> ~ <8> 2. The curable composition according to claim 1 . <10> <1> ~ <9> 2. A cured product obtained by curing the curable composition according to claim 1. <11> <10> A flat panel display comprising the cured product according to claim 1. <12> <10> A conformal coating comprising the cured product described in claim 1.

[0186] The contents described in each of the above items can be appropriately applied to other items. The present invention is not limited to the above-mentioned embodiments, and various modifications are possible within the scope of the claims. Therefore, embodiments obtained by appropriately combining the technical means disclosed in the different embodiments are also included in the technical scope of the present invention.

[0187] All of the journal and patent literature cited herein is hereby incorporated by reference.

[0188] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. EXAMPLES

[0189] [Synthesis Example 1: Synthesis of (meth)acrylic polymer (A1)] (preparation) 1000 g of n-butyl acrylate (corresponding to (meth)acrylic acid ester monomer (β), manufactured by Nippon Shokubai Co., Ltd.) was added to the container. 52.7 mg of copper(II) bromide (CuBr 2 , manufactured by Wako Pure Chemical Industries, Ltd.), 54.4 mg of hexamethyltris(2-aminoethyl)amine (Me 6 1.82 g of 100% dimethyl ether (TREN, Koei Chemical Industry Co., Ltd.) and 1.82 g of methanol (Wako Pure Chemical Industries Co., Ltd.) were added and stirred to obtain a homogeneous solution. This homogeneous solution is referred to as the "copper solution." The copper contained in the copper solution is equivalent to 15 ppm relative to the prepared n-butyl acrylate. In a separate container, 30.8 mL of methanol, 1.0 g of ascorbic acid (Wako Pure Chemical Industries Co., Ltd.) and 1.6 mL of triethylamine (Wako Pure Chemical Industries Co., Ltd.) were added and stirred for 30 minutes under a nitrogen stream to obtain a homogeneous solution. This homogeneous solution is referred to as the "ascorbic acid solution."

[0190] (1st step) Into a jacket temperature-adjusted stirring device, 19.02 g of ethyl α-bromobutyrate (0.0975 mol, manufactured by Tokyo Kasei Co., Ltd., initiator), 200 g of n-butyl acrylate (20% by weight of the total amount), 45.33 g of 3-(trimethoxysilyl)propyl methacrylate (0.195 mol, manufactured by Shin-Etsu Chemical Co., Ltd., 2.00 molar equivalent to the initiator), 108 g of methanol, and the total amount of the copper solution were charged, and stirred for 30 minutes under a nitrogen stream to obtain a homogeneous solution. At this time, the jacket temperature was set to 45°C. Next, when the temperature in the polymerization system reached 40°C or higher, the ascorbic acid solution was continuously dripped to start the polymerization reaction. The dripping rate of the ascorbic acid solution at this time was set to a rate at which 144 mg of ascorbic acid was added to the polymerization system per hour. When the temperature in the polymerization system was monitored, the temperature rose at the same time as the dripping of ascorbic acid began, and after reaching the maximum temperature, the temperature gradually decreased. After the temperature in the polymerization system reached the maximum temperature, the dripping rate of the ascorbic acid solution was changed to a rate of 48 mg of ascorbic acid per hour, and this dripping rate was maintained until the end of the polymerization. When the temperature in the polymerization system decreased and the difference with the jacket temperature became 1°C, a small amount of the reaction solution in the polymerization system was sampled and the second process was started. The sampled reaction solution was analyzed by gas chromatography, and it was found that 90% by weight of the n-butyl acrylate initially added had been consumed.

[0191] (2nd process) The remaining 800 g of n-butyl acrylate (80% by weight of the total amount) was continuously dropped into the polymerization system over a period of 90 minutes. Sampling was carried out successively, and the reaction was analyzed by gas chromatography. When 88% by weight of the total amount of n-butyl acrylate added to the polymerization system was consumed, the process moved to the third step.

[0192] (3rd step) 49.86 g of 3-(trimethoxysilyl)propyl methacrylate (0.215 mol, 2.20 molar equivalents relative to the initiator) was added to the polymerization system. When 98% by weight of the total amount of n-butyl acrylate added to the polymerization system was consumed, the dropwise addition of the ascorbic acid solution was stopped, and the polymerization was terminated.

[0193] (devolatilization) After the polymerization was completed, devolatilization was started and the jacket temperature was set to 80° C. Devolatilization was continued with a vacuum pump until 1 hour had elapsed after the temperature in the system reached 80° C., to obtain a polymer after devolatilization.

[0194] (purification) 1000g of butyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the polymer after devolatilization, and the mixture was mixed and stirred until a uniform solution was obtained, and an adsorbent was further added. Next, the mixture was stirred at a system temperature of 60°C for 2 hours, and then stirred at 80°C for 2 hours. As the adsorbent, 10g of Kyoward 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) and 10g of Kyoward 700SEN-S (manufactured by Kyowa Chemical Industry Co., Ltd.) were used. After the stirring was completed, the mixture obtained was filtered using a filter equipped with a bag filter cloth to obtain a clear polymer solution. 1.5g of an antioxidant (Sumilizer GS, Sumitomo Chemical Co., Ltd.) was added to this polymer solution and mixed until it became uniform. Then, the mixture was devolatilized at 110°C until the butyl acetate concentration was 500ppm or less, to obtain a (meth)acrylic polymer. This (meth)acrylic polymer corresponds to the (meth)acrylic polymer (A1) in this specification.

[0195] The number average molecular weight of the obtained polymer was about 13,000, and the molecular weight distribution was 1.1. The number of trimethoxysilyl groups introduced into the polymer was about 3.5 per molecule on average ( 1 1 H NMR analysis).

[0196] [Synthesis Example 2: Synthesis of (meth)acrylic polymer having dialkoxysilyl group] (Polymerization process) 100 parts by weight of n-butyl acrylate was prepared and deoxidized. The inside of a stainless steel reaction vessel equipped with a stirrer was deoxidized, and 0.84 parts by weight of cuprous bromide and 40 parts by weight of n-butyl acrylate were added and heated and stirred. 8.79 parts by weight of acetonitrile and 3.51 parts by weight of diethyl-2,5-dibromoadipate (initiator) were added and mixed. After adjusting the temperature of the mixed liquid to about 80°C, pentamethyldiethylenetriamine was added to start the polymerization reaction. The remaining 60 parts by weight of n-butyl acrylate were added one by one to advance the polymerization reaction. During the polymerization reaction, additional pentamethyldiethylenetriamine was appropriately added to adjust the polymerization rate. The total amount of pentamethyldiethylenetriamine used throughout the polymerization process was 0.15 parts by weight. In the polymerization process, the system was prevented from being overheated by the heat of polymerization, and the temperature in the system was adjusted to about 80 to about 90°C. When the polymerization reaction rate reached about 95% or more, the volatile matter was removed by devolatilization under reduced pressure to obtain a (meth)acrylic polymer.

[0197] (Diene reaction process) 21 parts by weight of 1,7-octadiene, 35 parts by weight of acetonitrile, and 0.68 parts by weight of pentamethyldiethylenetriamine were added to the (meth)acrylic polymer obtained through the polymerization process. The mixture was heated and stirred for several hours while controlling the temperature in the system to about 80°C to about 90°C, to react 1,7-octadiene with the terminals of the polymer. Acetonitrile and unreacted 1,7-octadiene were removed by devolatilization under reduced pressure, and a (meth)acrylic polymer having an alkenyl group at the terminal was obtained.

[0198] (Rough purification process) The (meth)acrylic polymer having an alkenyl group at the end obtained through the diene reaction process was diluted with toluene. 1 part by weight of a filter aid, 0.5 parts by weight of an adsorbent (Kyoward 700SEN, manufactured by Kyowa Chemical Industry Co., Ltd.), and 0.5 parts by weight of hydrotalcite (Kyoward 500SH, manufactured by Kyowa Chemical Industry Co., Ltd.) were added, and the mixture was heated and stirred at about 80 to 100°C, after which the solid components were filtered off. The filtrate was concentrated to obtain a crude product.

[0199] (purification process) 0.2 parts by weight of a heat stabilizer (Sumilizer GS: manufactured by Sumitomo Chemical Co., Ltd.) and an adsorbent (Kyoward 700SEN and Kyoward 500SH) were added to the crude product obtained through the crude production process. The temperature in the system was raised while the mixture obtained was subjected to reduced pressure devolatilization and heating and stirring. The mixture was subjected to reduced pressure devolatilization and heating and stirring for several hours at a high temperature of about 170 to about 200°C. Next, the adsorbent (Kyoward 700SEN and Kyoward 500SH) and toluene (about 10 times the weight of the polymer) were added, and the mixture was further heated and stirred for several hours at a high temperature of about 170 to about 200°C. The obtained treatment liquid was diluted with toluene, and the adsorbent was filtered off. The filtrate was concentrated to obtain a purified product ((meth)acrylic polymer having alkenyl groups at both ends).

[0200] (Silylation step) The purified product obtained through the purification step was mixed with 3.2 parts by weight of methyldimethoxysilane, 1.6 parts by weight of methyl orthoformate, and 0.0010 parts by weight of a platinum catalyst (an isopropanol solution of bis(1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst), and heated and stirred at about 100°C. After heating and stirring for about 1 hour, volatile matters such as unreacted methyldimethoxysilane were distilled off under reduced pressure to obtain a (meth)acrylic polymer having a dimethoxysilyl group at the end of the molecule. Since a dialkoxysilyl group was introduced into this polymer, it does not correspond to the (meth)acrylic polymer (A) in this specification.

[0201] The number average molecular weight of the obtained polymer was about 13,800, and the molecular weight distribution was 1.3. The number of dimethoxysilyl groups introduced into the polymer was about 1.8 per molecule on average ( 1 1 H NMR analysis).

[0202] [Synthesis Example 3: Synthesis of (meth)acrylic polymer (B)] (Polymerization process) 100 parts by weight of n-butyl acrylate was prepared and deoxidized. The inside of a stainless steel reaction vessel equipped with a stirrer was deoxidized, and 0.42 parts by weight of cuprous bromide and 20 parts by weight of n-butyl acrylate were added and heated and stirred. 8.8 parts by weight of acetonitrile and 3.5 parts by weight of diethyl 2,5-dibromoadipate (initiator) were added and mixed. After adjusting the temperature of the mixed liquid to about 80°C, 0.018 parts by weight of pentamethyldiethylenetriamine was added to start the polymerization reaction. The remaining 80 parts by weight of n-butyl acrylate were added one by one to advance the polymerization reaction. During the polymerization reaction, additional pentamethyldiethylenetriamine was appropriately added to adjust the polymerization rate. The total amount of pentamethyldiethylenetriamine used throughout the polymerization process was 0.17 parts by weight. In the polymerization process, the system was prevented from being overheated by the heat of polymerization, and the temperature in the system was adjusted to about 80 to about 90°C. When the polymerization reaction rate reached about 95% or more, an oxygen-nitrogen mixed gas was introduced into the gas phase of the reaction vessel. While maintaining the internal temperature of the system at about 80 to about 90°C, the reaction liquid was heated and stirred for several hours to bring the polymerization catalyst into contact with oxygen. Acetonitrile and unreacted monomers were removed by devolatilization under reduced pressure to obtain a (meth)acrylic polymer. The obtained (meth)acrylic polymer was colored dark green.

[0203] (purification process) The (meth)acrylic polymer obtained in the polymerization step was diluted with butyl acetate (about 100 parts by weight based on the polymer). A filter aid was added to the diluted solution, which was then heated and filtered. An adsorbent (Kyoward 700SEN and Kyoward 500SH) was added to the filtrate, which was then filtered again to obtain a clear liquid. The filtrate was concentrated to obtain a nearly colorless and transparent purified product.

[0204] (Acryloyl group introduction process) The polymer was dissolved in N,N-dimethylacetamide (about 100 parts by weight based on the polymer). Potassium acrylate (about 2 molar equivalents based on the Br group at the polymer end), a heat stabilizer (4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl), and an adsorbent (Kyoward 700SEN) were added, and the mixture was heated and stirred at about 70°C for several hours. After distilling off the N,N-dimethylacetamide under reduced pressure, the mixture was diluted again with butyl acetate (about 100 parts by weight based on the polymer), and a filter aid was added to filter out the solid content. The filtrate was concentrated to obtain a (meth)acrylic polymer (B) having an acryloyl group at the end. The polymer was colored brown.

[0205] The number average molecular weight of the obtained polymer (B) was about 12,000, and the molecular weight distribution was 1.1. The number of acryloyl groups introduced into the polymer was about 1.9 per molecule on average ( 1 1 H NMR analysis).

[0206] Materials used in the Examples and Comparative Examples Materials other than the (meth)acrylic polymer used in the following examples and comparative examples are as follows. Photoradical polymerization initiator (C) Benzophenone (Tokyo Chemical Industry Co., Ltd.) Omnirad379EG (IGM Resins BV, 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one) Condensation catalyst (D) AP-8 (2-ethylhexyl acid phosphate, manufactured by Daihachi Chemical Industry Co., Ltd.) 1,8-Diazabicyclo[5.4.0]undec-7-ene (Fujifilm Wako Pure Chemical Industries, Ltd.) ●(Meth)acrylic monomer (E) Viscoat #295 (Osaka Organic Chemical Industry, trimethylolpropane triacrylate) IBXA (Osaka Organic Chemical Industry, isobornyl acrylate) ●Silane coupling agent (F) ·KBM1003 (Shin-Etsu Chemical, vinyltrimethoxysilane) ·KBM5103 (Shin-Etsu Chemical, 3-acryloxypropyltrimethoxysilane) Anti-aging agent Nocrac CD (manufactured by Ouchi Shinko Chemical Industry, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine) Example 1 (Preparation of Curable Composition) Each component was mixed to obtain the composition shown in Table 1. Specifically, (meth)acrylic polymer (A1), (meth)acrylic polymer (B), Nocrac CD, Omnirad379EG, and benzophenone were added to a mayonnaise bottle and heated to 120°C. Then, Nocrac CD, Omnirad379EG, and benzophenone were dissolved while stirring occasionally with a spatula. Next, Viscoat #295, IBXA, KBM1003, and KBM5103 were added and stirred with a spatula. After leaving the mixture overnight, AP-8 and 1,8-diazabicyclo[5.4.0]undec-7-ene were added and stirred with a spatula. Furthermore, stirring (1,600 rpm x 1.5 minutes) and degassing (2,200 rpm x 3 minutes) were performed with a Thinky Mixer ARE-310 to obtain a curable composition.

[0207] (Mechanical properties of the cured product) The obtained curable composition was poured into a polypropylene mold to a thickness of 2 mm and allowed to stand. This allowed the curable composition to be degassed. A UV irradiation device (manufactured by Fusion UV Systems, model: LIGHT HAMMER 6, light source: mercury lamp, peak illuminance: 250 mW / cm 2 , Accumulated light intensity: 2,000mJ / cm 2 ) and then allowed to stand for 1 hour or 1 week under constant temperature and humidity of 23°C and 55% RH to obtain a sheet-like cured product.

[0208] From the obtained sheet-like cured product, a No. 3 dumbbell-shaped test piece as specified in JIS K 7113 was punched out. This test piece was subjected to a tensile test to measure the mechanical properties. Specifically, the stress at 10% elongation, the stress at break, and the elongation at break (elongation relative to the distance between chucks) were measured. The results are shown in Table 1. An autograph (AG-2000A, manufactured by Shimadzu Corporation) was used for the measurement, and the measurement temperature was 23°C and the tensile speed was 200 mm / min.

[0209] (Adhesion evaluation) The adhesive strength was measured using a glass test piece having a length of 100 mm, a width of 25 mm, and a thickness of 5 mm as a substrate. The obtained curable composition was applied to a thickness of 50 μm on a portion of the glass test piece up to 12.5 mm from the end, and a glass test piece of the same shape was bonded to the glass test piece. The obtained laminate was irradiated with UV light using a UV irradiation device (LIGHT HAMMER 6, manufactured by Fusion UV Systems). The irradiated UV light had a peak irradiance of 250 mW / cm. 2 , Accumulated light intensity: 2,000mJ / cm 2 The laminate was subjected to a tensile shear test at 23°C, 55% RH, and a tensile speed of 50 mm / min using an autograph (AG-2000A, manufactured by Shimadzu Corporation) (the test was carried out 1 hour and 1 week after the UV light irradiation). The results are shown in Table 1.

[0210] Comparative Example 1 A curable composition was obtained in the same manner as in Example 1, except that the (meth)acrylic polymer obtained in Synthesis Example 2 was used instead of the (meth)acrylic polymer (A1) obtained in Synthesis Example 1. A tensile shear test was performed in the same manner as in Example 1.

[0211] [Table 1]

[0212] 〔result〕 The difference between the cured product of Example 1 and the cured product of Comparative Example 1 is whether or not a trialkoxysilyl group-introduced (meth)acrylic polymer (A) was used. As can be seen from the results of the tensile test, it can be said that the cured product of Example 1 has higher strength than the cured product of Comparative Example 1. In addition, as can be seen from the results of the tensile shear test, the adhesiveness of the curable composition of Example 1 was superior to that of the curable composition of Comparative Example 1.

[0213] In particular, the results of the tensile test and tensile shear test performed 1 hour after UV irradiation can be regarded as evaluations of the mechanical properties and adhesive properties immediately after curing. In this respect, it is understood that the curable composition according to one embodiment of the present invention has excellent mechanical properties and adhesive properties (especially adhesive properties to glass) immediately after curing. [Industrial Applicability]

[0214] The curable composition according to one embodiment of the present invention can be used for flat panel displays, conformal coatings, and the like.

Claims

1. A (meth)acrylic polymer (A) having an average of 1.0 or more trialkoxysilyl groups per molecule at or near the terminals of the molecule; A (meth)acrylic polymer (B) having an average of 1.0 or more (meth)acryloyl groups per molecule at the molecular terminals; A photoradical polymerization initiator (C); A condensation catalyst (D); A curable composition comprising: The vicinity of the terminal of the molecule in the (meth)acrylic polymer (A) refers to a region in which 25% or less of the repeating units are located, counting from the terminal of the molecule, with the total number of repeating units contained in the molecule being 100%, The (meth)acrylic polymer (A) is a (meth)acrylic polymer (A1) that satisfies the following conditions: The (meth)acrylic polymer (A1) has an X block and a Y block; The molecule of the (meth)acrylic polymer (A1) contains an XY diblock structure or an XYX triblock structure in the molecule; the number of repeating units derived from a (meth)acrylic acid ester monomer having a trialkoxysilyl group contained in the X block is 1.0 or more on average; the content of a repeating unit derived from a (meth)acrylic acid ester monomer having a trialkoxysilyl group contained in the Y block is 0 to 3% by weight based on the weight of all repeating units contained in the Y block; The (meth)acrylic polymer (A1) has a molecular weight distribution (Mw / Mn) of 1.8 or less.

2. The curable composition according to claim 1, wherein the (meth)acrylic polymer (A1) has an average of more than 2.0 trialkoxysilyl groups per molecule.

3. The curable composition according to claim 1 or 2, wherein the (meth)acrylic polymer (A) has trialkoxysilyl groups in the vicinity of both ends of the molecule.

4. The curable composition according to any one of claims 1 to 3, wherein the (meth)acrylic polymer (B) has a molecular weight distribution (Mw / Mn) of 1.8 or less.

5. The curable composition according to any one of claims 1 to 4, further comprising a (meth)acrylic monomer (E).

6. The curable composition according to any one of claims 1 to 5, further comprising a silane coupling agent (F).

7. The curable composition according to any one of claims 1 to 6, wherein the trialkoxysilyl group is a trimethoxysilyl group.

8. The (meth)acrylic polymer (A) contains 50% by weight or more of repeating units derived from n-butyl acrylate based on the weight of all repeating units contained in the (meth)acrylic polymer (A). The curable composition according to any one of claims 1 to 7.

9. A cured product obtained by curing the curable composition according to any one of claims 1 to 8.

10. A flat panel display comprising the cured product according to claim 9.

11. A conformal coating comprising the cured product of claim 9.

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