JP2021116371A - Curable resin composition - Google Patents

Abstract

To provide a curable resin composition that is cured to provide a cured product which has excellent toughness and weather resistance.SOLUTION: A curable resin composition contains a vinyl polymer having crosslinkable functional groups. The vinyl polymer has two or more terminals, and at the main chain and the terminals of the vinyl polymer the crosslinkable functional groups are included.SELECTED DRAWING: None

Description

The present invention relates to a curable resin composition.

As a curable resin used for industrial applications, a vinyl-based copolymer having a crosslinkable functional group obtained by radical polymerization is well known. Such vinyl-based copolymers are used as curable resin compositions, and are widely used in the field of cured products such as paints, adhesives, pressure-sensitive adhesives, sealing materials, molding materials, and rubber sheets.
As a vinyl-based copolymer used in such a curable resin composition, Patent Document 1 describes vinyl having a hydrolyzable silyl group, which is obtained by continuously polymerizing a vinyl-based copolymer under high temperature conditions. System copolymers are disclosed. It is described that a cured product obtained from a curable resin composition containing this vinyl-based copolymer exhibits good breaking strength and breaking elongation.
Further, Patent Document 2 discloses a curable resin composition containing a vinyl-based polymer having crosslinkable silyl groups at both ends, which is obtained by living radical polymerization. It is described that this vinyl-based copolymer has a narrow molecular weight distribution, and the tensile properties of the cured product are superior to those of a cured product obtained from a general radical copolymer.

Japanese Unexamined Patent Publication No. 2006-45275 Japanese Unexamined Patent Publication No. 11-130931

However, although the vinyl-based polymer described in Patent Document 1 is synthesized by radical polymerization under specific conditions, reactive groups are randomly introduced into the molecular chain. Therefore, the molecular weight between the cross-linking points of the cured product is not uniform and has a wide distribution, so that there is a limit to the elongation at break and the improvement of toughness of the cured product.

The vinyl-based polymer described in Patent Document 2 is a telechelic polymer having a narrow molecular weight distribution and having crosslinkable silyl groups at both ends. However, since the cross-linking points are only at both ends, the reaction does not occur, and if there are ends that are not incorporated into the cross-linking, the polymer becomes a monofunctional polymer and does not contribute to the tensile properties, so there is still room for improvement from the viewpoint of the toughness of the cured product. there were.
Further, in applications such as sealing materials, there is a demand for a curable resin composition having excellent toughness and weather resistance of the cured product.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a curable resin composition having excellent toughness and weather resistance of a cured product obtained by curing.

As a result of diligent studies to solve the above problems, the present inventor has found that the curable resin composition contains a vinyl-based polymer having a crosslinkable functional group, and the number of the vinyl-based polymers is two or more. A curable resin composition having a terminal of the vinyl polymer and having a crosslinkable functional group at the main chain and the terminal of the vinyl polymer is prepared, and the cured product obtained by curing the curable composition is tough and weather resistant. I found it to be excellent in sex. Based on such findings, the present invention has been completed by further studies.

（式中、
Ｒは、酸素原子、窒素原子及び硫黄原子からなる群より選択される１種以上のヘテロ原子を有していてもよいｎ価の有機基を示す。
ｎは２以上の整数を示す。
Ｕ及びＷはそれぞれ、同一又は異なって、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^１、−Ｃ（＝Ｏ）Ｒ^１、−Ｃ（＝Ｓ）Ｒ^１、−Ｃ（＝Ｓ）ＯＲ^１、−Ｃ（＝Ｏ）ＳＲ^１、−Ｃ（＝Ｏ）ＮＨ_２、−Ｃ（＝Ｏ）ＮＨＲ^１、−Ｃ（＝Ｏ）Ｎ（Ｒ^１）_２、水素原子、ハロゲン原子、又は置換基を有していてもよいアルキル基を示す。或いは、Ｕ及びＷが互いに結合して、それぞれが結合する隣接する炭素原子と共に環を形成していてもよく、当該環は置換基を有していてもよい。
Ｖは、同一又は異なって、水素原子、Ｒ^１、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^１、−Ｃ（＝Ｏ）Ｒ^１、−Ｃ（＝Ｓ）Ｒ^１、−Ｃ（＝Ｓ）ＯＲ^１、−Ｃ（＝Ｏ）ＳＲ^１、−Ｃ（＝Ｏ）ＮＨ_２、−Ｃ（＝Ｏ）ＮＨＲ^１、−Ｃ（＝Ｏ）Ｎ（Ｒ^１）_２、−ＯＲ^１、−ＳＲ^１、−ＯＣ（＝Ｏ）Ｒ^１、−ＳＣ（＝Ｏ）Ｒ^１、又は−ＯＣ（＝Ｓ）Ｒ^１を示す。
Ｒ^１は、アルキル基、アルケニル基、アルキニル基、アリール基、ヘテロアリール基、シクロアルキル基、ヘテロシクロアルキル基、アラルキル基、ヘテロアリールアルキル基、又はポリマー鎖を示し、これらの基又は鎖は置換基を有していてもよい。Ｒ^１が複数存在する場合、それらは同一又は異なっていてもよい。
ｋは２以上の整数を示す。
ここで、Ｕ、Ｖ、及びＷからなる群より選択される少なくとも１種の基には架橋性官能基を含む。
Ｘは、同一又は異なって、架橋性官能基を含む基又は水素原子を示す。Ｘの全部又は一部が架橋性官能基を含む基である。）
で表される化合物である、［１］〜［５］のいずれかに記載の硬化性樹脂組成物。
［７］ 前記Ｕ、Ｖ、及びＷからなる群より選択される少なくとも１種の基に含まれる架橋性官能基、並びに、前記Ｘで示される基に含まれる架橋性官能基が、同一又は異なって、エポキシ基、水酸基、ホルミル基、カルボキシル基、スルホン酸基、イソシアナート基、架橋性シリル基、アミノ基、又は（メタ）アクリロイル基である、［６］に記載の硬化性樹脂組成物。
［８］ 前記Ｕ、Ｖ、及びＷからなる群より選択される少なくとも１種の基に含まれる架橋性官能基、並びに、前記Ｘで示される基に含まれる架橋性官能基が、同一である、［６］又は［７］に記載の硬化性樹脂組成物。
［９］ 前記ビニル系重合体の分子量分布（Ｍｗ／Ｍｎ）が２．０未満である、［１］〜［８］のいずれかに記載の硬化性樹脂組成物。
［１０］ 前記架橋性官能基が架橋性シリル基である、［１］〜［９］のいずれかに記載の硬化性樹脂組成物。
［１１］ さらに、架橋性シリル基を有するポリオキシアルキレン系重合体を含む、［１］〜［１０］のいずれかに記載の硬化性樹脂組成物。
［１２］ シーリング材用途として適用される、［１］〜［１１］のいずれかに記載の硬化性樹脂組成物。
［１３］ 前記［１］〜［１２］のいずれかに記載の硬化性樹脂組成物の硬化物。 That is, the present invention provides the curable resin composition shown below.
[1] A curable resin composition containing a vinyl-based polymer having a crosslinkable functional group, wherein the vinyl-based polymer has two or more ends, and the main chain and the terminal of the vinyl-based polymer. A curable resin composition having a crosslinkable functional group.
[2] The curable resin composition according to [1], wherein the average number of crosslinkable functional groups per molecule of the vinyl polymer is 2 to 30.
[3] The curable resin composition according to [1] or [2], wherein the average number of crosslinkable functional groups in the main chain per molecule of the vinyl polymer is 0.2 to 20.
[4] The curable resin composition according to any one of [1] to [3], wherein the average number of crosslinkable functional groups at the terminals per molecule of the vinyl polymer is 0.4 to 12. ..
[5] The crosslinkable functional group is selected from the group consisting of an epoxy group, a hydroxyl group, a formyl group, a carboxyl group, a sulfonic acid group, an isocyanato group, a crosslinkable silyl group, an amino group, and a (meth) acryloyl group. The curable resin composition according to any one of [1] to [4], which is one type.
[6] The vinyl-based polymer has the formula (5):

(During the ceremony,
R represents an n-valent organic group which may have one or more heteroatoms selected from the group consisting of oxygen atoms, nitrogen atoms and sulfur atoms.
n represents an integer of 2 or more.
U and W are the same or different, respectively, -CO ₂ H, -CO ₂ R ¹ , -C (= O) R ¹ , -C (= S) R ¹ , -C (= S) OR ¹ ,- C (= O) SR ¹ , -C (= O) NH ₂ , -C (= O) NHR ¹ , -C (= O) N (R ¹ ) ₂ , with hydrogen atom, halogen atom, or substituent Indicates an alkyl group which may be used. Alternatively, U and W may be bonded to each other to form a ring with adjacent carbon atoms to which they are bonded, and the ring may have a substituent.
V is the same or different, hydrogen atom, R ¹ , -CO ₂ H, -CO ₂ R ¹ , -C (= O) R ¹ , -C (= S) R ¹ , -C (= S) OR ¹ , -C (= O) SR ¹ , -C (= O) NH ₂ , -C (= O) NHR ¹ , -C (= O) N (R ¹ ) ₂ , -OR ¹ , -SR ¹ , It indicates -OC (= O) R ¹ , -SC (= O) R ¹ , or -OC (= S) R ^1.
R ¹ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a cycloalkyl group, a heterocycloalkyl group, an aralkyl group, a heteroarylalkyl group, or a polymer chain, and these groups or chains are substituted. It may have a group. If R ¹ is plurally present, they may be the same or different.
k represents an integer of 2 or more.
Here, at least one group selected from the group consisting of U, V, and W contains a crosslinkable functional group.
X represents a group or a hydrogen atom containing a crosslinkable functional group, which is the same or different. All or part of X is a group containing a crosslinkable functional group. )
The curable resin composition according to any one of [1] to [5], which is a compound represented by.
[7] The crosslinkable functional group contained in at least one group selected from the group consisting of U, V, and W and the crosslinkable functional group contained in the group represented by X are the same or different. The curable resin composition according to [6], which is an epoxy group, a hydroxyl group, a formyl group, a carboxyl group, a sulfonic acid group, an isocyanato group, a crosslinkable silyl group, an amino group, or a (meth) acryloyl group.
[8] The crosslinkable functional group contained in at least one group selected from the group consisting of U, V, and W and the crosslinkable functional group contained in the group represented by X are the same. , [6] or [7].
[9] The curable resin composition according to any one of [1] to [8], wherein the vinyl polymer has a molecular weight distribution (Mw / Mn) of less than 2.0.
[10] The curable resin composition according to any one of [1] to [9], wherein the crosslinkable functional group is a crosslinkable silyl group.
[11] The curable resin composition according to any one of [1] to [10], further comprising a polyoxyalkylene polymer having a crosslinkable silyl group.
[12] The curable resin composition according to any one of [1] to [11], which is applied as a sealing material application.
[13] A cured product of the curable resin composition according to any one of the above [1] to [12].

The curable resin composition of the present invention contains a vinyl-based polymer having two or more ends, and has a crosslinkable functional group at the main chain and the end of the vinyl-based polymer. Therefore, when the curable resin composition is cross-linked, the cross-linking reaction effectively proceeds between the vinyl-based polymers and inside the vinyl-based polymer.
Further, since the vinyl-based polymer is obtained by living radical polymerization (particularly RAFT polymerization), it has a small molecular weight distribution and has crosslinkable functional groups at the main chain and terminals, so that it has a higher crosslink density and homogeneous crosslinks. You can get a body. Therefore, the cured product obtained by curing the curable resin composition of the present invention is excellent in toughness and weather resistance.
When the curable resin composition further contains a polyoxyalkylene polymer having a crosslinkable silyl group, the cured product is more excellent in toughness and weather resistance.

Hereinafter, the present invention will be described in detail.
1. 1. Curable Resin Composition The curable resin composition of the present invention contains a vinyl-based polymer having a crosslinkable functional group.

(1) Vinyl-based polymer The vinyl-based polymer has two or more ends, and has a crosslinkable functional group at the main chain and the terminal of the vinyl-based polymer. In the vinyl-based polymer, the main chain means a structure containing a repeating unit derived from a vinyl-based monomer in the vinyl-based polymer, and the structure may be linear or branched. The end means a site that binds to the end of the main chain (usually a sulfur atom). The number of the terminals is usually 2 to 12, preferably 2 to 10, more preferably 2 to 8, still more preferably an integer of 2 to 6, and particularly preferably an integer of 2 to 4.

The crosslinkable functional group means a functional group that can be crosslinked by being subjected to a crosslinking reaction. For example, the same or different, epoxy group, hydroxyl group, formyl group, carboxyl group, sulfonic acid group, isocyanato group, crosslinkability. Examples thereof include a silyl group, an amino group, and a (meth) acryloyl group, and a crosslinkable silyl group is preferable in that the toughness and weather resistance of the cured product are particularly excellent.
Since the vinyl-based polymer has a crosslinkable functional group at its main chain and its terminal, the cross-linking reaction proceeds between the vinyl-based polymers and inside the vinyl-based polymer. Therefore, the cured product is excellent in toughness and weather resistance.

The lower limit of the average number of crosslinkable functional groups in the main chain per molecule of the vinyl polymer is, for example, 0.2 or more, preferably 0.3 or more, more preferably 0.4 or more, still more preferably. It is 0.5 or more, more preferably 1 or more, particularly preferably 1.5 or more, and the upper limit is, for example, 20 or less, preferably 15 or less, more preferably 12 or less, still more preferably 10 or less. , More preferably 9 or less, and particularly preferably 8 or less. The average number is usually 0.2 to 20, preferably 0.3 to 15, more preferably 0.4 to 12, still more preferably 0.5 to 10, and particularly preferably 1 to 9. be.

The average number of terminal crosslinkable functional groups per molecule of the vinyl polymer has a lower limit of, for example, 0.4 or more, preferably 0.5 or more, more preferably 1 or more, still more preferably 1. The number is 5.5 or more, particularly preferably 1.8 or more, and the upper limit is, for example, 12 or less, preferably 10 or less, and more preferably 8 or less. The average number is usually 0.4 to 12, preferably 0.5 to 10, more preferably 1 to 10, still more preferably 1.5 to 10, and particularly preferably 1.8 to 10. be.

The average number of crosslinkable functional groups per molecule of the vinyl polymer has a lower limit of, for example, 2 or more, preferably 2.1 or more, more preferably 2.2 or more, still more preferably 2.5. The number is, for example, 30 or less, preferably 25 or less, more preferably 20 or less, still more preferably 15 or less, and particularly preferably 10 or less. The average number is usually 2 to 30, preferably 2 to 25, more preferably 2 to 20, still more preferably 2.1 to 15, and particularly preferably 2.2. There are 10 to 10.
The average number of crosslinkable functional groups per molecule of these vinyl-based polymers can usually ^{be determined by 1} H-NMR measurement.

The vinyl-based polymer is a polymerization control agent having two or more thiocarbonylthio groups (particularly a RAFT agent), a vinyl-based monomer having a crosslinkable functional group, and a vinyl-based single having no crosslinkable functional group. A vinyl-based monomer containing a metric (hereinafter also referred to as "other vinyl-based monomer") is subjected to living polymerization to have two or more thiocarbonylthio groups at the terminals and a crosslinkable functional group on the main chain. A polymer having a group (P1) is obtained, the thiocarbonylthio group is converted to a mercapto group (-SH), and the mercapto group is further reacted with a compound having reactivity with a mercapto group having a crosslinkable functional group. It can be manufactured by allowing it to be produced. The vinyl-based polymer has a sulfide bond (-S-) between the main chain and the terminal due to the above-mentioned production method.

（式中、Ｒ、Ｕ、Ｖ、Ｗ、ｋ、Ｘ、及びｎは前記に同じ。） Examples of the vinyl-based polymer include compounds represented by the above formula (5).

(In the formula, R, U, V, W, k, X, and n are the same as described above.)

R represents an n-valent organic group which may have one or more heteroatoms selected from the group consisting of oxygen atoms, nitrogen atoms and sulfur atoms. The n-valent organic group represented by R has a carbon atom bonded to a carbon atom to which W is bonded, and the carbon atom is a living with a vinyl-based monomer having a crosslinkable functional group described later. It can serve as a starting point for radical polymerization (particularly RAFT polymerization) reactions. From the viewpoint of the reactivity of RAFT polymerization and the like, the ^{carbon atom is preferably bonded to the sp 2} hybrid orbital carbon atom or the sp hybrid orbital carbon atom contained in the organic group represented by R. As the sp ² hybridized carbon atoms or sp hybridized carbon atoms, e.g., carbon atoms on the aromatic ring, the carbon atoms on the heteroaromatic ring, a carbonyl group (C = O) carbon atoms, the carbon atoms of the cyano group Can be mentioned.

n is an integer of 2 or more, for example, an integer of 2 to 12, preferably an integer of 2 to 10, more preferably an integer of 2 to 8, still more preferably an integer of 2 to 6, and particularly preferably an integer of 2 to 4. It is an integer.

（式中、環Ａは、置換基を有していてもよい芳香環又は置換基を有していてもよいヘテロ芳香環を示し、Ｒ^ａ及びＲ^ｂは、同一又は異なって、水素原子、アルキル基、又はシアノ基を示し、ｐは２以上の整数を示し、ｑは０又は１を示し、ｒは１以上の整数を示す。） Specific examples of R include groups represented by the following formulas (5A) to (5C).

(In the formula, ring A represents an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent, ^{and Ra} and R ^b are the same or different, and the hydrogen atom. Indicates an alkyl group or a cyano group, p indicates an integer of 2 or more, q indicates 0 or 1, and r indicates an integer of 1 or more.)

Examples of the "aromatic ring" of the "aromatic ring which may have a substituent" represented by ring A include aromatic rings of C6 to C20 in which a single ring or two or more rings are fused. Examples of the aromatic ring include benzene, naphthalene, anthracene and the like. When the "aromatic ring" has a substituent, the substituents include, for example, an epoxy group, a hydroxyl group, an alkoxy group, an acyl group, an acyloxy group, a formyl group, an alkylcarbonyl group, a carboxyl group, a sulfonic acid group and an alkoxycarbonyl group. , Aryloxycarbonyl group, aryl group, isocyanato group, cyano group, silyl group, halogen atom, amino group, (meth) acryloyl group and the like. The "aromatic ring" may have one or more substituents selected from these substituents.

The "heteroaromatic ring" of the "heteroaromatic ring which may have a substituent" represented by ring A is composed of an oxygen atom, a nitrogen atom and a sulfur atom in which a single ring or two or more rings are fused. Examples thereof include C6 to C20 heteroaromatic rings having at least one heteroatom selected from the group. Examples of the heteroaromatic ring include a pyridine ring, a pyrazine ring, a pyrimidine ring, a thiazine ring and the like. When the "heteroaromatic ring" has a substituent, the substituents include, for example, an epoxy group, a hydroxyl group, an alkoxy group, an acyl group, an acyloxy group, a formyl group, an alkylcarbonyl group, a carboxyl group, a sulfonic acid group and an alkoxycarbonyl. Examples thereof include a group, an aryloxycarbonyl group, an aryl group, an isocyanato group, a cyano group, a silyl group, a halogen atom, an amino group, a (meth) acryloyl group and the like. The "heteroaromatic ring" may have one or more substituents selected from these substituents.

Examples of the "alkyl group" represented by or contained in R ^a and R ^b include linear or branched C1 to C20 (further C1 to C15, and even more C1 to C6, especially C1 to C3) alkyl groups. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a dodecyl group, a lauryl group and a stearyl group.

Examples of the "alkoxy group" represented by or contained in R ^a and R ^b include linear or branched C1 to C10 (further, C1 to C6, particularly C1 to C3) alkoxy groups. Examples of the alkoxy group include a methoxy group and an ethoxy group.

^{Examples of the "acyl group" represented by or contained in Ra} and R ^b include linear or branched acyl groups of C2 to C10 (further, C2 to C6, particularly C2 to C3). Examples of the acyl group include an acetyl group and a propanoyl group.

^{Examples of the "aryl group" represented by or contained in Ra} and R ^b include a monovalent aromatic hydrocarbon group in which a single ring or two or more rings of C6 to 10 are fused. Examples of the aryl group include a phenyl group, a toluyl group, a naphthyl group and the like.

p is preferably an integer of 2 to 10, and more preferably an integer of 2 to 4. p is the same as the definition of n above. q is preferably 1. r is preferably an integer of 1 to 20, and more preferably an integer of 1 to 10.

U and W are the same or different, -CO ₂ H, -CO ₂ R ¹ , -C (= O) R ¹ , -C (= S) R ¹ , -C (= S) OR ¹ , -C. It has (= O) SR ¹ , -C (= O) NH ₂ , -C (= O) NHR ¹ , -C (= O) N (R ¹ ) ₂ , hydrogen atom, halogen atom, or substituent. Indicates an alkyl group which may be present. Preferably, -CO ₂ H, -CO ₂ R ¹ , -C (= O) NH ₂ , -C (= O) NHR ¹ , -C (= O) N (R ¹ ) ₂ , hydrogen atom, C1- 3 Alkyl group and the like.

Alternatively, U and W may be bonded to each other to form a ring with adjacent carbon atoms to which they are bonded, and the ring may have a substituent.

（式中、Ｖは前記に同じ。）
当該環が有していてもよい置換基としては、例えば、アルキル基（特に、Ｃ１〜Ｃ６アルキル基）、水酸基、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^１、−Ｃ（＝Ｏ）Ｒ^１、−Ｃ（＝Ｓ）Ｒ^１、−ＣＳ（＝Ｏ）Ｒ^１、−Ｃ（＝Ｏ）ＳＲ^１、−ＣＮ、−Ｃ（＝Ｏ）ＮＨ_２、−Ｃ（＝Ｏ）ＮＨＲ¹、−Ｃ（＝Ｏ）ＮＲ^１ _２、−ＯＲ^１、−ＳＲ^１、−ＯＣ（＝Ｏ）Ｒ^１、−ＳＣ（＝Ｏ）Ｒ^１、−ＯＣ（＝Ｓ）Ｒ¹等が挙げられる。好ましくは、Ｃ１〜Ｃ３アルキル基等である。 When U and W are bonded to each other to form a ring together with adjacent carbon atoms to which they are bonded, examples of the ring include a cyclic ester (lactone ring), a cyclic acid anhydride, and a cyclic imide. Examples of the ring include the following rings. The ring may have a substituent.

(In the formula, V is the same as above.)
Examples of the substituent that the ring may have include an alkyl group (particularly, a C1 to C6 alkyl group), a hydroxyl group, -CO ₂ H, -CO ₂ R ¹ , -C (= O) R ¹ , and so on. -C (= S) R ¹ , -CS (= O) R ¹ , -C (= O) SR ¹ , -CN, -C (= O) NH ₂ , -C (= O) NHR ¹ , -C (= O) NR ¹ ₂ , -OR ¹ , -SR ¹ , -OC (= O) R ¹ , -SC (= O) R ¹ , -OC (= S) R ^{1, and the} like can be mentioned. Preferably, it is a C1-C3 alkyl group or the like.

V is a hydrogen atom, R ¹ , -CO ₂ H, -CO ₂ R ¹ , -C (= O) R ¹ , -C (= S) R ¹ , -C (= S) OR ¹ , -C ( = O) SR ¹ , -C (= O) NH ₂ , -C (= O) NHR ¹ , -C (= O) N (R ¹ ) ₂ , -OR ¹ , -SR ¹ , -OC (= O) ) R ¹ , -SC (= O) R ¹ , or -OC (= S) R ¹ . Preferably, a hydrogen atom, R ¹ , -CO ₂ H, -CO ₂ R ¹ , -C (= O) NH ₂ , -C (= O) NHR ¹ , -C (= O) N (R ¹ ) ₂ , -OC (= O) R ¹ etc.

R ¹ is the same or different, an alkyl group which may have a substituent (particularly, a C1 to C20 alkyl group), and an alkenyl group which may have a substituent (particularly, a C2 to C20 alkenyl group). , An alkynyl group which may have a substituent (particularly, a C2-C20 alkynyl group), an aryl group which may have a substituent (particularly, a C6-C10 aryl group), and a substituent. May have heteroaryl groups (particularly C3-C18 heteroaryl groups), cycloalkyl groups which may have substituents (particularly C3-C18 cycloalkyl groups), heterocyclos which may have substituents. Alkyl groups (particularly C2-C18 heterocycloalkyl groups), aralkyl groups which may have substituents (particularly C7 to C22 aralkyl groups), heteroarylalkyl groups which may have substituents (particularly). , C4-C22 heteroarylalkyl groups), or polymer chains that may have substituents (eg, polyalkylene oxides, polyarylene ethers, etc.).

As ^{one aspect of R 1} , C1 to C6 alkyl groups which may have a substituent, C6 to C20 alkyl groups which may have a substituent, and the like can be mentioned.

Examples of the ^{substituent that R 1} may have include an epoxy group, a hydroxyl group, an alkyl group (C1 to C6 alkyl group, etc.), an aryl group (phenyl group, toluyl group, etc.), and an alkoxy group (C1 to C6). Alkoxy group, etc.), formyl group, alkylcarbonyl group ((C1-C6 alkyl) carbonyl group, etc.), arylcarbonyl group (benzoyl group, etc.), carboxyl group, sulfonic acid group, alkoxycarbonyl group ((C1-C6 alkoxy) carbonyl) Groups, etc.), aryloxycarbonyl groups (phenoxycarbonyl groups, etc.), isocyanato groups, cyano groups, crosslinkable silyl groups, halogen atoms, amino groups, (meth) acryloyl groups and the like.

Among these substituents, the crosslinkable functional group includes, for example, an epoxy group, a hydroxyl group, a formyl group, a carboxyl group, a sulfonic acid group, an isocyanato group, a crosslinkable silyl group, an amino group, or a (meth) acryloyl group. In particular, a crosslinkable silyl group is preferable.

As used herein, the crosslinkable silyl group means a silicon-containing group that has a hydrolyzable group or a hydroxyl group on a silicon atom and can be crosslinked by forming a siloxane bond by hydrolysis. For example, a trialkoxysilyl group (tri-C1-C6 alkoxysilyl group, etc.), an alkyl (dialkoxy) silyl group (C1-C6alkyl (diC1-C6alkoxy) silyl group, etc.), a dialkyl (alkoxy) silyl group (diC1). ~ C6 alkyl (C1-C6 alkoxy) silyl group, etc.) and the like.

Preferred examples of R ¹ include an alkyl group having a crosslinkable silyl group, an alkyl group having an epoxy group, an alkyl group having an isocyanato group, an alkyl group having an amino group, an aryl group having a crosslinkable silyl group, and an epoxy group. Examples thereof include an aryl group having an aryl group, an aryl group having an isocyanato group, and an aryl group having an amino group.

k represents a number of 2 or more, usually 5 to 2,000, preferably 10 to 1,000, and more preferably 50 to 500. As will be described later, k can be arbitrarily set according to the degree of polymerization of the vinyl-based monomer (target number average molecular weight (Mn) and weight average molecular weight (Mw)).

X is a group containing a crosslinkable functional group. As will be described later, X is a group obtained by reacting a compound having a mercapto group represented by the formula (4) with a mercapto group having a crosslinkable functional group and a compound having reactivity. X can be represented, for example, as -L- (crosslinkable functional group) (in the formula, L represents a linker). The linker represented by L is a divalent group that links the crosslinkable functional group obtained in the above reaction with a sulfur atom, and is derived from various compounds having reactivity with the mercapto group used in the above reaction. Can be the basis.

At least one group selected from the group consisting of U, V, and W contains a crosslinkable functional group.

Here, the crosslinkable functional group includes a crosslinkable functional group such as an epoxy group, a hydroxyl group, a formyl group, a carboxyl group, a sulfonic acid group, an isocyanato group, a crosslinkable silyl group, an amino group, or a (meth) acryloyl group. means. Among these, a crosslinkable silyl group is preferable because the toughness and weather resistance of the cured product are particularly excellent.

（式中、Ｒ、Ｕ、Ｖ、Ｗ、ｋ、及びｎは前記に同じ。）
で表される構造を意味し、その末端とは、−Ｘで示される部位（基）を意味する。 In the compound represented by the formula (5), the main chain thereof is the formula (5D):

(In the formula, R, U, V, W, k, and n are the same as described above.)
It means the structure represented by, and the end thereof means the site (group) represented by -X.

The crosslinkable functional group contained in at least one group selected from the group consisting of U, V, and W, and the crosslinkable functional group contained in the group represented by X may be the same or different. , Preferably the same. In particular, it is preferable that they have the same crosslinkable silyl group.

The average number of crosslinkable functional groups per molecule of the vinyl polymer represented by the formula (5) is usually 2 to (15 + n), preferably 2.1 to (10 + n), and more. The number is preferably 2.1 to (9 + n), and particularly preferably 2.2 to (8 + n).
The average number of crosslinkable functional groups contained in the main chain represented by the formula (5D) per molecule of the vinyl polymer represented by the formula (5) is usually 0.2 to 20, which is preferable. Is 0.3 to 15, more preferably 0.4 to 12, still more preferably 0.5 to 10, and particularly preferably 1 to 9.
The average number of crosslinkable functional groups contained in the terminal (X) per molecule of the vinyl polymer represented by the formula (5) is usually 0.4 to the number of terminals (that is, n). The number is preferably 0.5 to n, more preferably 1 to n, still more preferably 1.5 to n, and particularly preferably 1.8 to n.
The average number of crosslinkable functional groups contained in the main chain and / or the terminal per molecule of the vinyl polymer can usually ^{be determined by 1} H-NMR measurement.

The weight average molecular weight (Mw) of the vinyl polymer is usually 2,000 to 1,000,000, preferably 5,000 to 500,000, and the number average molecular weight (Mn) is usually 2,000 to 1. It is in the range of 000,000, preferably 5,000 to 500,000. The molecular weight distribution (Mw / Mn) of the vinyl polymer is usually 1 or more and less than 2.0, preferably 1 to 1.9, more preferably 1 to 1.8, and particularly preferably 1 to 1. It is 1.7. The molecular weight can be determined by GPC (gel permeation chromatography) measurement (polystyrene conversion).

(2) Method for producing vinyl-based polymer The vinyl-based polymer contained in the curable resin composition of the present invention has two or more ends, and has a crosslinkable function on the main chain of the vinyl-based polymer and the ends. It is characterized by having a group. The vinyl polymer is, for example,
(I) A vinyl-based simple compound containing a vinyl-based monomer having a crosslinkable functional group and other vinyl-based monomers using a polymerization control agent having two or more thiocarbonylthio groups (particularly, a RAFT agent). A step of polymerizing a polymer (living radical polymerization) to obtain a vinyl polymer (P1) having a crosslinkable functional group in the main chain and one thiocarbonylthio group at each of two or more ends.
(Ii) A vinyl-based weight obtained by reacting the vinyl-based polymer (P1) obtained in step (i) with a nucleating agent and having one mercapto group (-SH) at each of two or more ends. The main chain is obtained by reacting the vinyl polymer (P2) obtained in the step of obtaining the coalescence (P2) and the step (iii) step (ii) with a mercapto group having a crosslinkable functional group and a compound having a reactivity. It can be produced by a production method including a step of obtaining a vinyl-based polymer (P3) having a crosslinkable functional group at the terminal and having a crosslinkable functional group at the terminal. Hereinafter, steps (i) to (iii) will be described.

Process (i):
In step (i), in the presence of a polymerization initiator, a polymerization control agent having two or more thiocarbonylthio groups is used to obtain a vinyl-based monomer having a crosslinkable functional group and other vinyl-based monomers. The containing vinyl-based monomer is polymerized (living radical polymerization) to obtain a vinyl-based polymer (P1) having a crosslinkable functional group in the main chain and a thiocarbonylthio group at two or more ends. This reaction can be carried out in the presence or absence of a solvent.

When a solvent is used, a known solvent usually used for the polymerization reaction can be used. Examples thereof include nitrile solvents, aromatic hydrocarbon solvents, ether solvents, ketone solvents, ester solvents, orthoester solvents, dimethylformamide, dimethyl sulfoxide, alcohol and water.
Specific examples of the nitrile solvent include acetonitrile, isobutyronitrile, benzonitrile and the like.
Specific examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and the like.
Specific examples of the ether solvent include anisole, dibutyl ether, tetrahydrofuran and the like.
Specific examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like.
Specific examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate and the like.
Specific examples of the orthoester solvent include trimethyl orthoacetate, triethyl orthoate, triethyl orthoate (n-propyl), tri (isopropyl) orthoate, trimethyl orthoacetate, triethyl orthoacetate, triethyl orthopropionate, ortho n-. Examples thereof include trimethyl butyrate and trimethyl orthoisobutyrate.
As the solvent, one type or a combination of two or more types can be used.
This reaction may be carried out in the form of bulk polymerization or the like without using a solvent.

（式中、Ｕ、Ｗ、及びＶは前記に同じ。但し、Ｕ及びＷが互いに結合して、それぞれが結合する隣接する炭素原子（−Ｃ＝Ｃ−）と共に環を形成していてもよく、当該環は置換基を有していてもよい。） The vinyl-based monomer used for the polymerization is capable of living radical polymerization (particularly RAFT polymerization), needs to contain a vinyl-based monomer having a crosslinkable functional group, and has a crosslinkable functionality. It preferably contains a vinyl-based monomer having a group and other vinyl-based monomers. Examples of the vinyl-based monomer include a compound represented by the formula (2) or a salt thereof. The compound represented by the formula (2) or a salt thereof contains a vinyl-based monomer having a crosslinkable functional group, and further contains one or more vinyl-based monomers having a crosslinkable functional group, and It is preferable that one or more (and two or more) other vinyl-based monomers are contained.

(In the formula, U, W, and V are the same as described above. However, U and W may be bonded to each other to form a ring together with adjacent carbon atoms (-C = C-) to which they are bonded. , The ring may have a substituent.)

（式中、Ｖは前記に同じ。）
当該環が有していてもよい置換基としては、アルキル基（特に、Ｃ１−３アルキル基）、水酸基、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^１、−Ｃ（＝Ｏ）Ｒ^１、−Ｃ（＝Ｓ）Ｒ^１、−ＣＳ（＝Ｏ）Ｒ^１、−Ｃ（＝Ｏ）ＳＲ^１、−ＣＮ、−Ｃ（＝Ｏ）ＮＨ_２、−Ｃ（＝Ｏ）ＮＨＲ¹、−Ｃ（＝Ｏ）ＮＲ^１ _２、−ＯＲ^１、−ＳＲ^１、−ＯＣ（＝Ｏ）Ｒ^１、−ＳＣ（＝Ｏ）Ｒ^１、−ＯＣ（＝Ｓ）Ｒ¹等が挙げられる。Ｒ^１は前記に同じ。 When U and W are bonded to each other to form a ring with adjacent carbon atoms (-C = C-) to which they are bonded, the rings include cyclic ester (lactone ring), cyclic acid anhydride, and cyclic imide. And so on. Examples of the compound represented by the formula (2) having the ring include the following compounds or salts thereof. The ring may have a substituent.

(In the formula, V is the same as above.)
Substituents that the ring may have include alkyl groups (particularly C1-3 alkyl groups), hydroxyl groups, -CO ₂ H, -CO ₂ R ¹ , -C (= O) R ¹ , -C. (= S) R ¹ , -CS (= O) R ¹ , -C (= O) SR ¹ , -CN, -C (= O) NH ₂ , -C (= O) NHR ¹ , -C (=) O) NR ¹ ₂ , -OR ¹ , -SR ¹ , -OC (= O) R ¹ , -SC (= O) R ¹ , -OC (= S) R ^{1, and the} like. R ¹ is the same as above.

Examples of the compound represented by the formula (2) or a salt thereof include maleic anhydride, N-alkylmaleimide, N-arylmaleimide, dialkylfumaric acid, and (meth) acrylic acid ester (the ester has a crosslinkable silyl). It may have a crosslinkable functional group such as a group), (meth) acrylic acid or a salt thereof, styrene, (meth) acrylamide, (meth) acrylonitrile, and a mixture of these monomers.

Specific examples of the compound represented by the formula (2) or a salt thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic. Alkyl (meth) acrylates such as 2-ethylhexyl acid, tetradecyl (meth) acrylate, octadecyl (meth) acrylate; cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate, cyclohexyl (meth) acrylate; (Meta) acrylic acid; (meth) acrylic acid aralkyl such as (meth) benzyl acrylate; (meth) acrylic acid aryl such as phenyl (meth) acrylic acid; (meth) acrylonitrile; styrene such as alpha-methylstyrene and styrene. Compounds; (meth) epoxyalkyl acrylates such as glycidyl (meth) acrylate; (meth) acrylic acids such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. Hydroxyalkyl; N, N-dialkylaminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate; triethylene glycol (meth) acrylate. Etc. (meth) acrylic acid (poly) alkylene glycol; itaconic acid anhydride, itaconic acid; (meth) acrylamide; N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-tert-butyl ( N-alkyl (meth) acrylamides such as meta) acrylamide, Nn-butyl (meth) acrylamide, N-tert-butyl (meth) allylamide, Nn-butyl (meth) allylamide; N- (hydroxymethyl) ( N- (hydroxyalkyl) (meth) acrylamide such as meta) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide; vinyl benzoate compounds such as vinyl benzoate, alpha-methyl vinyl benzoate; diethylaminoalpha-methyl Dialkylaminostyrene compounds such as styrene and diethylaminostyrene; vinylbenzene sulfonic acid compounds such as p-vinylbenzene sulfonic acid and sodium salt of p-vinylbenzene sulfonic acid; trimethoxysilylpropyl (meth) acrylate, tri (meth) acrylate Triisopropoxysilylpropyl (meth) acrylate, tributoki (meth) acrylate Trialkoxysilylalkyl (meth) acrylates such as cysilylpropyl; dimethoxymethylsilylpropyl (meth) acrylate, diethoxymethylsilylpropyl (meth) acrylate, diisopropoxymethylsilylpropyl (meth) acrylate, (meth) (Meta) Dialkoxyalkylsilylalkyl acrylates such as dibutoxymethylsilylpropyl acrylate; Vinyl acetate; Vinyl halides such as vinyl chloride, vinyl fluoride, vinyl bromide; Maleic anhydride; N-phenylmaleimide and the like Examples thereof include N-arylmaleimide; N-alkylmaleimide such as N-butylmaleimide; N-vinylpyrrolidone; N-vinylcarbazole and the like. When the group contained in each compound contains an isomer, the group is interpreted as containing any isomer.

The salt of the compound represented by the formula (2) is not particularly limited as long as it does not adversely affect the reaction of the present invention. For example, salts with alkali metals such as lithium, sodium and potassium; salts with alkaline earth metals such as magnesium and calcium; salts with amines such as ammonia, monoalkylamines, dialkylamines and trialkylamines; tetrabutylammonium. Examples thereof include salts with tetraalkylammonium and the like.

The vinyl-based monomer having a crosslinkable functional group contained in the compound or salt represented by the formula (2) is at least one selected from the group consisting of U, V, and W in the formula (2). A compound or salt having a crosslinkable functional group at the group of. As the crosslinkable functional group, a crosslinkable silyl group is preferable. The crosslinkable functional group and the crosslinkable silyl group can be selected from the above.

Among the compounds represented by the formula (2) or salts thereof, specific examples of the vinyl-based monomer having the crosslinkable functional group include epoxyalkyl (meth) acrylate such as glycidyl (meth) acrylate; (Meta) hydroxyalkyl (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylic acid, hydroxypropyl (meth) acrylic acid, hydroxybutyl (meth) acrylic acid; (meth) acrylic acid such as triethylene glycol (meth) acrylic acid (meth) Poly) alkylene glycol; N- (hydroxyalkyl) (meth) acrylamide such as N- (hydroxymethyl) (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide; p-vinylbenzene sulfonic acid, p- Vinylbenzene sulfonic acid compounds such as vinylbenzene sulfonic acid sodium salt; (meth) acrylic acid trimethoxysilylpropyl, (meth) acrylic acid triethoxysilylpropyl, (meth) acrylic acid triisopropoxysilylpropyl, (meth) acrylic acid Trialkoxysilylpropyl (meth) acrylate, such as tributoxysilylpropyl, dimethoxymethylsilylpropyl (meth) acrylate, diethoxymethylsilylpropyl (meth) acrylate, diisopropoxymethylsilylpropyl (meth) acrylate, Dialkoxyalkylsilylalkyl (meth) acrylic acid such as dibutoxymethylsilylpropyl (meth) acrylic acid; (meth) acrylic acid and the like can be mentioned.

From the viewpoint of tensile properties, the amount of the vinyl-based monomer having a crosslinkable functional group in the total amount of the vinyl-based monomer to be polymerized is usually 0.05 to 5 mol%, preferably 0.05 to 5 mol%. It is 0.1 to 2.5 mol%, more preferably 0.2 to 1.5 mol%. In particular, when the crosslinkable functional group is a crosslinkable silyl group, the amount of the vinyl-based monomer having a crosslinkable silyl group in the total amount of the vinyl-based monomer is usually 0.1 to 2.5 mol. %, Preferably 0.2 to 1.5 mol%.

The polymerization initiator is not particularly limited as long as it produces free radicals usually used for living radical polymerization (RAFT polymerization). Examples thereof include thermal polymerization initiators (peroxides, peroxides, azo compounds, etc.); photopolymerization initiators; redox polymerization initiators, and the like. Further, a free radical generation means using high-energy radiation such as electron beam, X-ray, gamma ray or the like may be used.

Examples of the thermal polymerization initiator include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-cyanobutane), dimethyl 2,2'-azobis (isobutyrate), 4,4'-. Azobis (4-cyanovalerian acid), 1,1'-azobis (cyclohexanecarbonitrile) (ACHN), 2,2'-azobis (2-methylbutyronitrile) (ABN-E), 2- (t-butylazo ) -2-Cyanopropane, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis [2-methyl -N- (2-Hydroxyethyl) propionamide] (AMHP), 4,4'-azobis (4-cyanopentanoic acid) (ACPA), 2,2'-azobis (5-hydroxy-2methylpentanenitrile) ( AHPN), 2,2'-azobis (N, N'-dimethyleneisobutyramidine) dihydrochloride, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (N, N'- Dimethyleneisobutyramidine), 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis {2-methyl- N- [1,1-bis (hydroxymethyl) -2-ethyl] propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (Isobutylamide) dihydrate, 2,2'-azobis (2,2,4-trimethylpentane), 2,2'-azobis (2-methylpropane), t-butylperoxyacetate, t-butylper Oxybenzoate, t-butylperoxyneodecanoate, t-butylperoxyisobutyrate, t-amylperoxypivalate, t-butylperoxypivalate, diisopropylperoxydicarbonate, dicyclohexylperoxydicarbonate, Dicumyl peroxide, dibenzoyl peroxide (BPO), dilaurolyl peroxide (LPO), potassium peroxydisulfate, ammonium peroxydisulfate, tert-butyl 2-ethylhexaneperoxoate, di-t -Butyl hyponitrite, dicumyl hyponitrite and the like can be mentioned. One of these, or a combination of two or more, can be selected.

As the photopolymerization initiator, for example, a benzene derivative, a benzophenone, an acylphosphine oxide, and a photooxidation-reduction system are selected.

Examples of the redox polymerization initiator include the following oxides (potassium, peroxydisulfate, hydrogen peroxide, t-butylhydroperoxide, etc.) and reducers (iron (II), titanium (III), thio). A combination of potassium sulfate, potassium hydrogen peroxide, etc.) can be mentioned.

As other suitable polymerization initiators and methods, known ones can be adopted.

Examples of the polymerization initiator that is easily dissolved in a hydrophilic solvent include 4,4-azobis (cyanovalerian acid) and 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl)-. 2-Hydroxyethyl] propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (N, N'-dimethyleneisobutylamidine), 2,2'-azobis (N, N'-dimethyleneisobutylamidine) dihydrochloride, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis {2-methyl-N- [1 , 1-bis (hydroxymethyl) -2-ethyl] propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (isobutylamide) Examples include, but are not limited to, dihydrates and derivatives thereof.

Examples of the polymerization initiator that is easily dissolved in a hydrophobic solvent include azo compounds, and examples thereof include known substances 2,2'-azobisisobutyronitrile.
Other suitable initiator compounds include acyl peroxides such as acetyl peroxide and benzoyl peroxide, and alkyl peroxides such as t-butyl α-cumyl peroxide. Hydroperoxides such as t-butyl hydroperoxide and cumyl hydroperoxide can also be used.

The amount of the polymerization initiator used can be appropriately set according to various conditions such as the type and amount of the vinyl-based monomer, and is not particularly limited. For example, from the viewpoint of obtaining a polymer having a smaller molecular weight distribution, the amount of the radical polymerization initiator used per 1 mol of the polymerization control agent (particularly RAFT agent) having 2 or more thiocarbonylthio groups is 0.5 mol or less. It is preferably 0.2 mol or less, and more preferably 0.2 mol or less. Further, from the viewpoint of stably performing the polymerization reaction, the amount of the radical polymerization initiator used with respect to 1 mol of the polymerization control agent is preferably 0.001 mol or more, and more preferably 0.005 mol or more. .. Therefore, the amount of the radical polymerization initiator used with respect to 1 mol of the polymerization control agent is preferably in the range of 0.001 mol or more and 0.5 mol or less, and more preferably in the range of 0.005 mol or more and 0.2 mol or less.

The reaction temperature during the polymerization reaction is preferably 30 ° C. or higher and 120 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and further preferably 50 ° C. or higher and 100 ° C. or lower. When the reaction temperature is 30 ° C. or higher, the polymerization reaction can proceed smoothly. On the other hand, when the reaction temperature is 120 ° C. or lower, side reactions can be suppressed and restrictions on the initiators and solvents that can be used are relaxed.

（式中、Ｚは、−Ｒ^Ａ、−ＳＲ^Ａ、−ＯＲ^Ａ、又は−ＮＲ^ＡＲ^Ｂで示される基であり、Ｒ^Ａ及びＲ^Ｂは、同一又は異なって、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいヘテロアリール基、又は置換基を有していてもよいアラルキル基を示す。Ｚが−ＮＲ^ＡＲ^Ｂで示される基のとき、Ｒ^Ａ及びＲ^Ｂは互いに結合してそれぞれが結合する窒素原子と共に環を形成していてもよく、当該環は置換基を有していてもよい。２以上のＺは、同一又は異なっていてもよい。Ｒ及びｎは前記に同じ。）
で表される化合物又はその塩が挙げられる。 Examples of the polymerization control agent having two or more thiocarbonylthio groups include the formula (1):

^(Wherein, Z is a group represented by ^{-R A, -SR A, -OR A} , or ^-NR A ^{R B, R A} and ^{R B} are the same or different, have a substituent Indicates an alkyl group which may have an alkyl group, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or an aralkyl group which may have a substituent. Z is -NR. when the group represented by ^a R ^B, R ^a and R ^B may form a ring together with the nitrogen atom to which each bonded to are bonded to each other, .2 the ring which may have a substituent The above Z may be the same or different. R and n are the same as described above.)
Examples thereof include a compound represented by (1) or a salt thereof.

As "alkyl group" of the "optionally substituted alkyl group" represented by R ^A and ^{R B,} C1 to C20 linear or branched (further C1 to C15, further more C1 -C10, especially Examples thereof include the alkyl groups of C1 to C6). Examples of the "alkyl group" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group. , Undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, lauryl group, stearyl group and the like. When the "alkyl group" has a substituent, the substituents include, for example, an epoxy group, a hydroxyl group, an alkoxy group, an acyl group, an acyloxy group, a formyl group, an alkylcarbonyl group, a carboxyl group, a sulfonic acid group and an alkoxycarbonyl group. , Aryloxycarbonyl group, isocyanato group, cyano group, silyl group, halogen atom, amino group and the like. The "alkyl group" may have one or more substituents selected from these substituents.

As the "aryl group" of the "optionally substituted aryl group" represented by R ^A and R ^B, it means a monovalent group obtained by removing one hydrogen atom from an aromatic hydrocarbon, e.g. , C6 to C20 aryl groups in which a single ring or two or more rings are fused. Examples of the "aryl group" include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthrasenyl group and the like. When the "aryl group" has a substituent, the substituents include, for example, an epoxy group, a hydroxyl group, an alkoxy group, an acyl group, an acyloxy group, a formyl group, an alkylcarbonyl group, a carboxyl group, a sulfonic acid group and an alkoxycarbonyl group. , Aryloxycarbonyl group, isocyanato group, cyano group, silyl group, halogen atom, amino group and the like. The "aryl group" may have one or more substituents selected from these substituents.

As "heteroaryl group" of the "heteroaryl group optionally having a substituent" represented by R ^A and R ^B, refers to a monovalent group derived by removing one hydrogen atom from heteroaromatic hydrocarbons Then, for example, a heteroaryl group of C5 to C20 in which a single ring or two or more rings are fused can be mentioned. Examples of the "heteroaryl group" include a pyridyl group, a quinolyl group, an isoquinolyl group, a pyrimidinyl group and the like. When the "heteroaryl group" has a substituent, the substituents include, for example, an epoxy group, a hydroxyl group, an alkoxy group, an acyl group, an acyloxy group, a formyl group, an alkylcarbonyl group, a carboxyl group, a sulfonic acid group and an alkoxycarbonyl. Examples thereof include a group, an aryloxycarbonyl group, an isocyanato group, a cyano group, a silyl group, a halogen atom and an amino group. The "heteroaryl group" may have one or more substituents selected from these substituents.

As "aralkyl group" of "optionally substituted aralkyl group" represented by R ^A and R ^B, 1 or more hydrogen atoms on the above-mentioned "alkyl group" substituted by the above "aryl group" Means a group. When the "aralkyl group" has a substituent, examples of the substituent include those listed as the substituents of the above-mentioned "alkyl group" and "aryl group".

When the group Z is represented by -NR ^A R ^B, as the ring formed together with the nitrogen atom to which each bound R ^A and R ^B together are attached, the nitrogen atom is neutral and cationic constituting the ring For example, pyrrole ring, pyrazole ring, imidazole ring, pyrrolidine ring, piperidine ring, piperazine ring, pyridine ring, pyrimidine ring, pyrazine ring, oxazole ring, thiazole ring, morpholine ring, thiazine ring, triazole ring and the like. Can be mentioned. When the ring has a substituent, the substituent includes, for example, an alkyl group (C1 to C6 alkyl group, etc.), an oxo group (= O), an epoxy group, a hydroxyl group, an alkoxy group, an acyl group, an acyloxy group, and a formyl. Examples thereof include a group, an alkylcarbonyl group, a carboxyl group, a sulfonic acid group, an alkoxycarbonyl group, an aryloxycarbonyl group, an isocyanato group, a cyano group, a silyl group, a halogen atom and an amino group. The ring may have one or more substituents selected from these substituents.

Z is preferably the group represented by -SR ^A.

The n-valent organic group represented by R has a carbon atom bonded to the group represented by -SC (= S) -Z, and the carbon atom is a living with a vinyl-based monomer. It can serve as a starting point for radical polymerization (particularly RAFT polymerization) reactions. From the viewpoint of the reactivity of RAFT polymerization and the like, the ^{carbon atom is preferably bonded to the sp 2} hybrid orbital carbon atom or the sp hybrid orbital carbon atom contained in R. As the sp ² hybridized carbon atoms or sp hybridized carbon atoms, e.g., carbon atoms on the aromatic ring, the carbon atoms on the heteroaromatic ring, a carbonyl group (C = O) carbon atoms, the carbon atoms of the cyano group Can be mentioned.

The compound represented by the formula (1) or a salt thereof is a known method, for example, Macromolecules 2003, 36, 2273-2283, Macromolecules 2005, 38, 9518-9525, Macromolecules 2007, 40, 4446-4455, Macromolecules 2012, 45, 4205-4215, J. Am. Chem. Soc. 2008, 130, 12242-12243, J. Am. Chem. Soc. 2011, 133, 15707-15713, Produced in accordance with Japanese Patent No. 6174036, etc. be able to.

（式中、環Ａ、Ｒ^ａ、Ｒ^ｂ、ｐ、ｑ、ｒ、Ｒ^Ａ、及びＺは前記に同じ。２以上のＲ^Ａは、同一又は異なっていてもよく、２以上のＺは、同一又は異なっていてもよい。） Specific examples of the embodiment of the compound represented by the formula (1) or the salt thereof include the compounds represented by the following formulas (1A) to (1C) or salts thereof.

(Wherein ring ^{A, R a, R b,} p, q, r, R A, and Z is ^{R A} of the same .2 above said, which may be the same or different, two or more Z is It may be the same or different.)

The amount of the polymerization control agent (RAFT agent) having two or more thiocarbonylthio groups is not particularly limited, and can be appropriately set according to the target number average molecular weight (Mn).

The living radical polymerization reaction is preferably carried out in an atmosphere of an inert gas containing no oxygen. The reaction temperature during the polymerization reaction is preferably 40 ° C. or higher and 100 ° C. or lower, more preferably 45 ° C. or higher and 90 ° C. or lower, and further preferably 50 ° C. or higher and 80 ° C. or lower. When the reaction temperature is 40 ° C. or higher, the polymerization reaction can proceed smoothly. On the other hand, when the reaction temperature is 100 ° C. or lower, side reactions can be suppressed and restrictions on the initiators and solvents that can be used are relaxed.

（式中、ｋは２以上の数を示し、他の記号は前記に同じ。） One form of step (i) can be expressed as follows. That is, it is represented by the formula (3) by polymerizing the vinyl-based monomer represented by the formula (2) using the RAFT agent represented by the formula (1) in the presence of the polymerization initiator. A vinyl-based polymer (P1) can be produced.

(In the formula, k indicates a number of 2 or more, and other symbols are the same as above.)

k can be arbitrarily set according to the degree of polymerization (target number average molecular weight (Mn)). U, V and W can be converted to the desired functional group in step (i) or by an additional step.

After completion of the reaction, it is isolated or purified using a known treatment method such as reprecipitation treatment or vacuum drying, and vinyl having a crosslinkable functional group in the main chain and a thiocarbonylthio group at two or more ends. A system polymer (P1) can be obtained.

（式中、Ｙは脱離基を示し、他の記号は前記に同じ。） All of the compounds represented by the above formulas (1A) to (1C) can be produced by a known method. For example, it can be manufactured as follows.

(In the formula, Y indicates a leaving group, and the other symbols are the same as above.)

Examples of the leaving group represented by Y include a halogen atom (chlorine atom, bromine atom, etc.) and the like.
The compound represented by the formula (1A) can be produced by reacting the compound represented by the formula (6), the compound represented by the formula (7) and carbon disulfide (CS ₂ ). For example, it can be produced according to or according to Preparation Examples 2 and 3.

The compound represented by the formula (1B) can be produced by subjecting the compound represented by the formula (8) and the compound represented by the formula (9) to a condensation reaction. For example, it can be produced according to or according to a known dehydration esterification reaction.

The compound represented by the formula (1C) can be produced by subjecting the compound represented by the formula (8) and the compound represented by the formula (10) to a condensation reaction. For example, it can be produced according to or according to a known dehydration esterification reaction.

Process (ii):
In step (ii), usually in the presence of a solvent, the vinyl polymer (P1) obtained in step (i) is reacted with a nucleophile to remove thiocarbonyl groups, and two or more. A vinyl polymer (P2) having a mercapto group (-SH) is obtained.

As the solvent, a known solvent usually used for the nucleophilic reaction can be used. Examples thereof include nitrile solvents, aromatic hydrocarbon solvents, ether solvents, ketone solvents, ester solvents, orthoester solvents, dimethylformamide, dimethyl sulfoxide, alcohol and water.
Specific examples of the nitrile solvent include acetonitrile, isobutyronitrile, benzonitrile and the like.
Specific examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and the like.
Specific examples of the ether solvent include anisole, dibutyl ether, tetrahydrofuran and the like.
Specific examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like.
Specific examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate and the like.
Specific examples of the orthoester solvent include trimethyl orthoacetate, triethyl orthoate, triethyl orthoate (n-propyl), tri (isopropyl) orthoate, trimethyl orthoacetate, triethyl orthoacetate, triethyl orthopropionate, ortho n-. Examples thereof include trimethyl butyrate and trimethyl orthoisobutyrate.
These can be used alone or in combination of two or more.

The nucleophile is not particularly limited as long as it can convert a thiocarbonylthio group into a mercapto group. Examples thereof include nucleophiles such as ammonia, amine compounds, metal alkoxides (sodium methoxide, sodium ethoxide, etc.), and thiol compounds. Of these, amine compounds such as primary or secondary amine compounds are preferable. Specific examples thereof include ethylamine, n-propylamine, isopropylamine, butylamine, hexylamine, octylamine, benzylamine, ethylenediamine, hydrazine, piperidine, aminoethanol, and combinations thereof.

The amount of the nucleophile to be used can be appropriately selected according to the molar equivalent of the thiocarbonylthio group contained in the vinyl polymer (P1). From the viewpoint of reaction efficiency, the molar equivalent of the nucleophile with respect to the thiocarbonylthio group is preferably 1 molar equivalent or more, more preferably 10 molar equivalent or more, and particularly preferably 20 molar equivalent or more. Further, from the viewpoint that the influence of the odor by the unreacted nucleophile is small, 70 molar equivalents or less is preferable, 60 molar equivalents or less is further preferable, and 50 molar equivalents or less is particularly preferable.

Such a reaction of removing a thiocarbonyl group from a vinyl polymer (P1) having two or more thiocarbonylthio groups using an amine compound may be referred to as amino decomposition.

When the thiocarbonyl group is removed by amino decomposition, it is preferable that oxygen is removed from the reaction system so that the mercapto group produced is not oxidized to form a disulfide (SS). For example, along with the removal of oxygen, a reducing agent can be supplied to a solution of the vinyl polymer (P1) to suppress disulfide formation.

As the reducing agent, tributylphosphine, tris (2-carboxyethyl) phosphine _{(TCEP), NaBH 4, LiBH} (C 2 H 5) 3 , etc. borohydride used with tributylphosphine, dimethyl phenyl phosphine (DMPP), nitrous Examples include sodium dithionite (Na ₂ S ₂ O ₄ ), sodium bisulfite (NaHSO ₃ ), ethylenediaminetetra (acetic acid) (EDTA), and combinations thereof.

The reaction temperature is preferably 10 ° C. or higher, more preferably 15 ° C. or higher, and particularly preferably 25 ° C. or higher from the viewpoint of reaction efficiency. Further, from the viewpoint that side reactions such as a nucleophilic reaction on the polymer main chain are unlikely to occur, 80 ° C. or lower is preferable, 60 ° C. or lower is further preferable, and 50 ° C. or lower is particularly preferable.

From the viewpoint of reaction efficiency, the reaction time is preferably 1 hour or longer, more preferably 2 hours or longer, and particularly preferably 3 hours or longer. Further, from the viewpoint that side reactions such as a nucleophilic reaction on the polymer main chain are unlikely to occur, it is preferably 48 hours or less, more preferably 36 hours or less, and particularly preferably 24 hours or less.

The progress of the reaction can be monitored, for example, as follows. A part of the solution was withdrawn, the solution was reprecipitated, purified and vacuum dried to prepare a sample, and ¹ H-NMR measurement showed a peak derived from a proton on the carbon to which the RAFT group (thiocarbonylthio group) was bonded. Disappeared, and it was observed that a proton-derived peak on the carbon to which the formed SH group was bonded appeared. The number of SH groups per molecule can be confirmed from this peak integral value and the peak integral value derived from a characteristic proton (for example, a hydrogen atom on a benzene ring) existing at the starting end.

（式中、記号は前記に同じ。） One form of step (ii) can be expressed as follows. That is, the vinyl polymer (P2) represented by the formula (4) can be produced by reacting the nucleophile with the vinyl polymer (P1) represented by the formula (3).

(In the formula, the symbols are the same as above.)

After completion of the reaction, isolation or purification is performed using a known treatment method such as reprecipitation treatment or vacuum drying to obtain a vinyl polymer (P2) having two or more mercapto groups, and further step (iii). ) Can be provided. Alternatively, a solution containing a vinyl-based polymer (P2) having two or more mercapto groups obtained in this reaction can be used in step (iii) without isolation or purification.

Step (iii):
In the step (iii), a compound having reactivity with a mercapto group having a crosslinkable functional group with respect to the vinyl polymer (P2) obtained in the step (ii), usually in a solvent (hereinafter, “crosslinkability”). A vinyl polymer (P3) having a crosslinkable functional group in the main chain and a crosslinkable functional group at two or more ends by reacting with a mercapto group-reactive compound having a functional group. To manufacture.

As the solvent, a known solvent can be used. Examples thereof include nitrile solvents, aromatic hydrocarbon solvents, ether solvents, ketone solvents, ester solvents, orthoester solvents, dimethylformamide, dimethyl sulfoxide, alcohol and water.
Specific examples of the nitrile solvent include acetonitrile, isobutyronitrile, benzonitrile and the like.
Specific examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and the like.
Specific examples of the ether solvent include anisole, dibutyl ether, tetrahydrofuran and the like.
Specific examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like.
Specific examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate and the like.
Specific examples of the orthoester solvent include trimethyl orthoacetate, triethyl orthoate, triethyl orthoate (n-propyl), tri (isopropyl) orthoate, trimethyl orthoacetate, triethyl orthoacetate, triethyl orthopropionate, ortho n-. Examples thereof include trimethyl butyrate and trimethyl orthoisobutyrate.
These can be used alone or in combination of two or more.

Examples of the mercapto group-reactive compound in the mercapto group-reactive compound having a crosslinkable functional group include (meth) acryloyl group-containing compound, epoxy group-containing compound, isocyanate group-containing compound, and alkenyl group-containing compound. Examples of the crosslinkable functional group contained in this compound include an epoxy group, a hydroxyl group, a formyl group, a carboxyl group, a sulfonic acid group, an isocyanato group, a crosslinkable silyl group, an amino group and a (meth) acryloyl group. Can be mentioned. Of these, a crosslinkable silyl group is preferable. The compound may have one or more crosslinkable functional groups. The crosslinkable functional group and the crosslinkable silyl group can be selected from those described above.

Specific examples of the mercapto group-reactive compound having a crosslinkable functional group include a (meth) acryloyl group in a molecule such as 1,4-butanediol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate. Compounds having (meth) acryloyl group and isocyanate group in the molecule such as 2-isocyanatoethyl (meth) acrylate and 2-isocyanatoethyl (meth) acrylate; Compounds having (meth) acryloyl group and epoxy group; Compounds having (meth) acryloyl group and alkenyl group in the molecule such as allyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid Compounds having (meth) acryloyl group and hydroxyl group in the molecule such as 3-hydroxypropyl; Compounds having (meth) acryloyl group and carboxyl group in the molecule such as (meth) acrylic acid; γ- (meth) acryloyloxypropyl Compounds having (meth) acryloyl group and crosslinkable silyl group in the molecule such as trimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane; 1,4- Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether A compound having two or more epoxy groups in the molecule; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycyl Compounds having an epoxy group and a crosslinkable silyl group in the molecule such as sidoxypropylmethyldimethoxysilane; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, etc. Compounds having an isocyanate group and a crosslinkable silyl group in the molecule; Compounds having an alkenyl group and a hydroxyl group in the molecule such as allyl alcohol and 3-butene-1-ol; Alkenyl groups and carboxyl in the molecule such as 6-heptenoic acid Examples include compounds having a group.

The amount of the mercapto group-reactive compound having a crosslinkable functional group can be appropriately selected according to the molar equivalent of the mercapto group contained in the vinyl-based polymer (P2), for example, a vinyl-based polymer (P2). It is usually 0.1 to 50 molar equivalents, preferably 0.5 to 20 molar equivalents, relative to 1 molar equivalent of the mercapto group contained in P2).

In this reaction, it is preferable that oxygen is removed from the reaction system so that the mercapto group contained in the vinyl polymer (P2) is not oxidized to form disulfide (SS). For example, the reducing agent described in step (ii) above can be included.

This reaction can be carried out at 0 to 200 ° C., preferably room temperature to 150 ° C. for 1 to 24 hours. After completion of the reaction, isolation or purification is performed using a known treatment method such as reprecipitation treatment or vacuum drying to obtain a vinyl polymer (P3) having a crosslinkable functional group at the main chain and two or more ends. be able to.

The weight average molecular weight (Mw) of the vinyl polymer is usually 2,000 to 1,000,000, and the number average molecular weight (Mn) is usually 2,000 to 1,000,000. The molecular weight distribution (Mw / Mn) of the vinyl polymer is usually 1 or more and less than 2.0, preferably 1 to 1.9. The molecular weight can be determined by GPC (gel permeation chromatography) measurement (polystyrene conversion).

（式中、記号は前記に同じ。） One form of step (iii) can be expressed as follows. That is, by reacting the polymer (P2) represented by the formula (4) with a compound having reactivity with a mercapto group, the main chain represented by the formula (5) and two or more ends are crosslinked. A vinyl-based polymer (P3) having a functional group can be produced.

(In the formula, the symbols are the same as above.)

2. Curable Resin Composition and Cured Product The curable resin composition of the present invention contains a vinyl polymer (P3) having a crosslinkable functional group at the main chain and the terminal, and may contain other components as necessary. good. Examples of other components contained in the composition include a polyoxyalkylene polymer having a crosslinkable functional group, a curing catalyst, a crosslinker, a plasticizer, a filler, an antiaging agent, an adhesive imparting agent and the like.

The curable resin composition of the present invention can be cured by using a curing catalyst to obtain a cured product. When curing, a cross-linking agent may be further added to cure. The cross-linking agent can be selected according to the type of the cross-linking functional group at the main chain and the terminal contained in the vinyl polymer (P3).

Examples of the curing catalyst include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, and the like. Dibutyltin diisooctylmalate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diisooctyl Tetravalent tin compounds such as malate; titanates such as tetrabutyl titanate and tetrapropyl titanate; organic aluminum compounds such as aluminum trisacetylacetonate, aluminumtrisethylacetate, diisopropoxyaluminum ethylacetate; zirconium tetra Chelate compounds such as acetylacetonate and titaniumtetraacetylacetonate; lead octylate; butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, Benzylamine, diethylaminopropylamine, xylylene diamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholin, N-methylmorpholin, 2-ethyl-4-methylimidazole, 1 , 8-Diazabicyclo (5,4,5) undecene-7 (DBU) and other amine compounds; or salts of these amine compounds with carboxylic acids, etc .; low molecular weight obtained from excess polyamines and polybasic acids. Polyamide resin; reaction product of excess polyamine and epoxy compound; silanol condensation of silane coupling agent having an amino group such as γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane Catalysts; known silanol condensation catalysts such as other acidic and basic catalysts; known quaternary ammonium salts such as tetrabutylammonium bromide; peroxide compounds such as benzoyl peroxide; dialkyls such as zinc diethyldithiocarbamate Zinc dithiocarbamate; dimethyl dithiocarbamine Examples thereof include dialkyldithiocarbamate iron (III) such as iron (III) acid.

The amount of the curing catalyst used is not particularly limited, and is usually 0.05 to 5 parts by mass, preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the vinyl polymer (P3).

When a cross-linking agent is used, the cross-linking agent can be appropriately selected depending on the type of the cross-linking functional group at the terminal of the vinyl-based polymer (P3).

When the crosslinkable functional group contained in the vinyl polymer (P3) is a (meth) acryloyl group, it is usually preferably cured by irradiation with active energy rays such as ultraviolet rays, visible rays and electron beams or heat.
When the curable resin composition is cured by active energy rays, it is preferable to contain a known photopolymerization initiator as a curing catalyst, and when the curable resin composition is cured by heat, it is cured. It preferably contains a known thermal polymerization initiator as the catalyst.
As a cross-linking agent, a dithiol compound such as 1,2-ethanedithiol, 1,4-butanedithiol, 1,10-decandithiol, 1,4-benzenedithiol, or ethane-1,1,1-trithiol, 1,3 The en-thiol reaction can be utilized by using a polyhydric thiol such as a trithiol compound such as 5-benzenetrithiol.

When the crosslinkable functional group contained in the vinyl polymer (P3) is an epoxy group, an ammonium salt of an organic carboxylic acid, a dithiocarbamate, a polyvalent carboxylic acid, an anhydride or the like is preferably used as the crosslinking agent.
Examples of the ammonium salt of organic carboxylic acid include ammonium benzoate and the like.
Examples of the dithiocarbamate include zinc salts such as dimethyldithiocarbamic acid, diethyldithiocarbamic acid and dibenzyldithiocarbamic acid, iron salts and tellurium salts.
Examples of the polyvalent carboxylic acid include malonic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, citric acid, tartaric acid, phthalic acid and the like.

When the crosslinkable functional group contained in the vinyl polymer (P3) is a carboxyl group, a polyvalent amine, a polyfunctional isocyanate, a polyfunctional epoxy compound or the like is preferably used as the crosslinking agent.
Examples of the polyvalent amine include aliphatic diamine compounds such as hexamethylenediamine, hexamethylenediamine carbamate, N, N'-dicinnamylidene-1,6-hexanediamine; and alicyclic type such as 4,4'-methylenebiscyclohexylamine carbamate. Diamine compounds; 4,4'-methylene dianiline, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-(m-phenylenediisopropylidene) dianiline, 4,4'-(p-phenylenedi) Isopropylidene) dianiline, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 4,4'-diaminobenzanilide, m-xylylene diamine, p-xylylene diamine, 1,3,5 Examples thereof include aromatic diamine compounds such as −benzenetriamine and 1,3,5-benzenetriaminomethyl.
Examples of the polyfunctional isocyanate include hexamethylene diisocyanate, dimethyldiphenylenediisocyanate, and isophorone diisocyanate.
Examples of the polyfunctional epoxy compound include aromatic epoxy compounds such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, phenol novolac type epoxy resin, and cresol novolac type epoxy resin; dicyclopentadiendioxide, 3,4-epoxy. Alicyclic epoxy compounds such as cyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate; aliphatics such as diglycidyl ether of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol Epoxy compounds and the like can be mentioned.

When the crosslinkable functional group contained in the vinyl polymer (P3) is a hydroxyl group, the crosslinking agent includes a polyfunctional isocyanate, a methylolated melamine, an aminoplast resin such as an alkyl ether product thereof or a hypocondensed product, and a polyfunctional product. Carboxylic acid and its halides are preferably used.

When a cross-linking agent is used, the amount of the cross-linking agent used is not particularly limited, and is usually 0.01 to 30 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the vinyl polymer (P3). be.

When the crosslinkable functional group contained in the vinyl polymer (P3) is a crosslinkable silyl group, a crosslinker reaction occurs due to moisture in the air, so that it is usually not necessary to add a crosslinking agent or the like. .. However, from the viewpoint of excellent compatibility of the present curable resin composition and excellent mechanical properties (toughness) and weather resistance of the cured product, a polyoxyalkylene polymer having a crosslinkable silyl group (hereinafter, simply "poly"). It is also preferable to contain (also referred to as "oxyalkylene polymer").

The polyoxyalkylene polymer is not particularly limited as long as it contains a repeating unit represented by the following formula (11).
-O-R ^2- (11)
(In the formula, R ² is a divalent hydrocarbon group.)

^{Examples of R 2} in the above formula (11) include the following.
-(CH ₂ ) _s- (s is an integer from 1 to 10)
-CH (CH ₃ ) CH _2-
-CH (C ₂ H ₅ ) CH _2-
・ -C (CH ₃ ) ₂ CH _2-

The polyoxyalkylene polymer may contain one or a combination of two or more of the above repeating units. Among these, −CH (CH ₃ ) CH ₂ − is preferable in terms of excellent workability.

The crosslinkable silyl group contained in the polyoxyalkylene polymer is not particularly limited, and examples thereof include an alkoxysilyl group, a halogenosilyl group, and a silanol group, but an alkoxysilyl group is preferable from the viewpoint of easy control of reactivity. Specific examples of the alkoxysilyl group include a trimethoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, a triethoxysilyl group, a methyldiethoxysilyl group, a dimethylethoxysilyl group and the like.

The polyoxyalkylene polymer can be produced by a known method. For example, a polymerization method using an alkali catalyst such as KOH, a polymerization method using a transition metal compound-porphyrin complex catalyst, a polymerization method using a composite metal cyanide complex catalyst, a polymerization method using phosphazene, etc. using the corresponding epoxy compound or diol as a raw material. Can be manufactured using.
The polyoxyalkylene polymer may be either a linear polymer or a branched polymer. Moreover, you may use these in combination.

The average value of the number of crosslinkable silyl groups contained in one molecule of the polyoxyalkylene polymer is preferably in the range of 1 to 4 from the viewpoint of mechanical properties and adhesiveness of the cured product, and more preferably. It is in the range of 1.5 to 3.

The position of the crosslinkable silyl group contained in the polyoxyalkylene polymer is not particularly limited, and may be the side chain and / or the terminal of the polymer.
Further, the polyoxyalkylene polymer may be either a linear polymer or a branched polymer. Moreover, you may use these in combination.

The number average molecular weight (Mn) of the polyoxyalkylene polymer is preferably 5,000 or more, more preferably 10,000 or more, and further preferably 15,000 or more from the viewpoint of mechanical characteristics. Mn may be 18,000 or more, 22,000 or more, or 25,000 or more. The upper limit of Mn is preferably 60,000 or less, more preferably 50,000 or less, and further preferably 40,000 or less from the viewpoint of workability (viscosity) at the time of coating the curable resin composition. be. The range of Mn can be set by combining the above upper limit value and lower limit value, and may be, for example, 5,000 or more and 60,000 or less, 15,000 or more and 60,000 or less, and 18 It may be 000 or more and 50,000 or less, and may be 22,000 or more and 50,000 or less. The number average molecular weight can be determined by GPC measurement (polystyrene conversion).

The mass ratio of the vinyl-based copolymer to the polyoxyalkylene-based polymer is preferably 10/90 to 90/10, more preferably 20/80 to 80/20, and more preferably 30/70. ~ 70/30.

A commercially available product may be used as the polyoxyalkylene polymer. Specific examples include "MS Polymer S203", "MS Polymer S303", "MS Polymer S810", "Cyril SAT200", "Cyril SAT350", "Cyril EST280" and "Cyril SAT30" manufactured by Kaneka Corporation, and AGC. Examples thereof include "Exester ES-S2410", "Exester ES-S2420" and "Exester ES-S3430" (all trade names) manufactured by Co., Ltd.

Examples of the plasticizer include a liquid polyurethane resin, a polyester plasticizer obtained from dicarboxylic acid and a diol; an etherified product or an esterified product of polyalkylene glycol such as polyethylene glycol and polypropylene glycol; a saccharide polyhydric alcohol such as sucrose, and ethylene. Polyether-based plasticizers such as saccharide-based polyethers obtained by addition polymerization of alkylene oxides such as oxides and propylene oxides and then etherification or esterification; polystyrene-based plasticizers such as poly-α-methylstyrene; crosslinkable properties. Examples thereof include poly (meth) acrylates having no functional group. Among these, poly (meth) acrylate having no crosslinkable functional group is preferable in terms of durability such as weather resistance of the cured product. Among these, those having an Mw in the range of 1,000 to 7,000 and a glass transition temperature of −30 ° C. or lower are more preferable.
The amount of the plasticizer used is preferably in the range of 0 to 100 parts by mass with respect to 100 parts by mass of the total amount of the vinyl-based polymer or 100 parts by mass of the total amount of the vinyl-based polymer and the polyoxyalkylene-based polymer. It may be in the range of 0 to 80 parts by mass, or may be in the range of 0 to 50 parts by mass.

As the filler, light calcium carbonate having an average particle size of about 0.02 to 2.0 μm, heavy calcium carbonate having an average particle size of about 1.0 to 5.0 μm, titanium oxide, carbon black, synthetic silicic acid, talc, etc. Examples thereof include zeolite, mica, silica, calcined clay, kaolin, bentonite, aluminum hydroxide, barium sulfate, glass balloon, silica balloon, and polymethyl methacrylate balloon. With these fillers, the mechanical properties of the cured product can be improved, and the tensile strength and tensile elongation can be improved.
Among these, light calcium carbonate, heavy calcium carbonate and titanium oxide, which have a high effect of improving physical properties, are preferable, and a mixture of light calcium carbonate and heavy calcium carbonate is more preferable.
The amount of the filler added is preferably 20 to 300 parts by mass with respect to 100 parts by mass of the total amount of the vinyl-based polymer or 100 parts by mass of the total amount of the vinyl-based polymer and the polyoxyalkylene-based polymer. Preferably, it is 50 to 200 parts by mass. In the case of a mixture of light calcium carbonate and heavy calcium carbonate as described above, the mass ratio of light calcium carbonate / heavy calcium carbonate is preferably in the range of 90/10 to 50/50.

Antioxidants include ultraviolet absorbers such as benzophenone compounds, benzotriazole compounds and oxalic acid anilides compounds, light stabilizers such as hindered amine compounds, antioxidants such as hindered phenols, heat stabilizers, or An anti-aging agent, which is a mixture of these, can be used.
Examples of the ultraviolet absorber include the trade names "Tinubin 571", "Tinubin 1130", and "Tinubin 327" manufactured by BASF. Examples of the light stabilizer include the product names "Tinubin 292", "Tinubin 144", and "Tinubin 123" manufactured by the same company, and the product name "Sanol 770" manufactured by Sankyo Co., Ltd. Examples of the heat stabilizer include the trade names "Irganox 1135", "Irganox 1520", and "Irganox 1330" manufactured by BASF. The trade name "Chinubin B75" manufactured by BASF, which is a mixture of an ultraviolet absorber / a light stabilizer / a heat stabilizer, may be used.

Examples of the adhesive-imparting agent include aminosilanes such as the trade names "KBM602", "KBM603", "KBE602", "KBE603", "KBM902", and "KBM903" manufactured by Shin-Etsu Silicone Co., Ltd.

In addition, a dehydrating agent such as methyl orthoacetate, methyl orthoacetate, vinylsilane, an organic solvent, or the like may be blended.
Further, another curable resin or thermoplastic resin may be added for the purpose of adjusting the performance, coatability, processability, etc. of the curable resin composition of the present invention. Specific examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, styrene resins of polystyrene, vinyl resins such as polyvinyl chloride, polyester resins, and polyamide resins. Moreover, you may add and mix known elastomers.

The curing catalyst, reaction temperature and reaction time of this curing reaction may be appropriately set according to the type of the terminal crosslinkable functional group contained in the vinyl polymer (P3), and can be easily set by those skilled in the art. be able to.

The curable resin composition of the present invention can be prepared as a one-component type that cures by preliminarily blending and sealing all the compounding components and absorbing the moisture in the air after application. Further, components such as a curing catalyst, a cross-linking agent, a filler, a plasticizer, and water are separately prepared as a compounding material, and the compounding material and a vinyl polymer are mixed as a two-component type before use. You can also do it. Of these, the one-component type is more preferable because it is easy to handle and there are few mistakes in mixing and mixing at the time of application.

The obtained cured product has excellent toughness and weather resistance. The cured product can be suitably used for applications in a wide range of fields such as automobile parts, home appliances and OA equipment parts, medical equipment parts, packaging materials, civil engineering and construction materials, electric wires, miscellaneous goods, and the like. Among these, it can be suitably used depending on the use of civil engineering and construction materials, and among these, it can be suitably used for applications such as sealing materials and adhesives for exterior tiles.

Hereinafter, the present disclosure will be specifically described based on Examples. The present disclosure is not limited to these examples. In the following, "parts" and "%" mean parts by mass and% by mass unless otherwise specified.
The methods for analyzing the polymers obtained in the synthetic example, the comparative synthetic example, the production example, and the comparative production example are described below.

<Molecular weight measurement>
The obtained polymer was subjected to gel permeation chromatography (GPC) measurement under the conditions described below to obtain a number average molecular weight (Mn) and a weight average molecular weight (Mw) in terms of polystyrene. Moreover, the molecular weight distribution (Mw / Mn) was calculated from the obtained values.
[Measurement condition]
Column: Tosoh TSKgel SuperMultipore HZ-M x 4 Solvent: Tetrahydrofuran Temperature: 40 ° C
Detector: RI
Flow velocity: 600 μL / min

<Preparation and evaluation method of curable resin composition>
Each component was blended according to the blending ratios (blended A and blended B) shown in Table 1 below to prepare a curable resin composition according to a conventional method.

The abbreviations in Table 1 mean the following.
-Polyoxyalkylene polymer X: Cyrilized at both ends of polypropylene glycol described in Preparation Example 1 below-UP-1110: Acrylic plasticizer, ARUFON (registered trademark) UP-1110 (manufactured by Toagosei Co., Ltd.)
・ Light calcium carbonate: Shiraishi Calcium CCR (manufactured by Shiraishi Calcium)
・ Heavy calcium carbonate: Super SS (manufactured by Maruo Calcium)
-R820: Titanium oxide R-820 (manufactured by Ishihara Sangyo Co., Ltd.)
-B75: Anti-aging agent, Tinubin B75 (manufactured by BASF)
-SH6020: Aminosilane, SH6020 (manufactured by Toray Dow Corning)
-SZ6300: Vinylsilane, SZ6300 (manufactured by Toray Dow Corning)
-U-220H: Tin catalyst (dibutyltin diacetylacetonate), Neostan U-220H (manufactured by Nitto Kasei Co., Ltd.)

<Tensile test>
Each curable resin composition (formulations A and B) was applied to a Teflon® sheet at room temperature (25 ° C.) at 23 ° C. and 50% RH for 6 days, then at 50 ° C. in a saturated steam atmosphere. It was cured for a day to prepare a cured sheet (cured product) having a thickness of 2 mm. A dumbbell for tensile test (JIS K 6251 No. 3 type) was prepared from the obtained cured product with a thickness of 2 mm, and the elongation at break [EL (%)] and elongation at break [EL (%)] by a tensile tester (Autograph AGS-J, manufactured by Shimadzu Corporation). The breaking strength [Ts (MPa)] was measured. The measurement was carried out at a tensile speed of 200 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50%.
In addition, the tensile product was calculated as follows.
Tension product = elongation at break [EL (%)] x strength at break [Ts (MPa)] / 2

<Weather resistance test>
Each curable resin composition (formulation B) is applied to a Teflon (registered trademark) sheet at room temperature (25 ° C.) and cured at 23 ° C. and 50% RH for 6 days, and then at 50 ° C. for 1 day in a saturated steam atmosphere. A cured sheet (cured product) having a thickness of 2 mm was prepared. The obtained cured product having a thickness of 2 mm was placed in a metal weather meter (“DAIPLA METAL WEATHER KU-R5NCI-A” manufactured by Daipla Wintes), and an accelerated weather resistance test was conducted. The conditions were irradiation 63 ° C., 70% RH, illuminance 80 mW / cm ^2, and the test was carried out once every two hours in a shower for 2 minutes. The time when abnormalities such as cracks began to occur in the appearance was recorded.

(1) Production of polyoxyalkylene polymer
Preparation Example 1 (Production of Polyoxyalkylene Polymer X)
Zinc hexacyanocobaltate glyme complex (0.05 g), polypropylene glycol (Mn: 2000, 50 g), and propylene glycol (510 g) were placed in a pressurized stirring tank reactor equipped with an oil jacket and having a capacity of 1000 mL, and heated to 120 ° C. It was heated and reacted until there was no pressure change. Then, the mixture was vacuum heated at 120 ° C. for 1 hour to distill off volatile components. Then, a 28% methanol solution (12.6 g) of sodium methoxide was added, the pressure was reduced at 100 ° C. for 1 hour, and methanol was distilled off. Then, allyl chloride (5.2 g) was added, and heating was performed at 100 ° C. for 2 hours. Then, the reaction solution was washed twice with water (300 ml) to remove salts. After dehydration by vacuum heating at 100 ° C. for 2 hours, chloroplatinic acid hexahydrate (0.02 g) and methyldimethoxysilane (8.3 g) were added and reacted for 4 hours to form a silylated product at both ends of polypropylene glycol. Hereinafter, it is also referred to as “polyoxyalkylene polymer X”). As a result of GPC measurement, Mn: 22,900 and Mw: 25,200.

≪Synthesis of RAFT agent≫
Preparation Example 2 (Synthesis of bifunctional RAFT agent DLBTTC)
(Synthesis of 1,4-bis (n-dodecylsulfanylthiocarbonylsulfanylmethyl) benzene)
1-Dodecanethiol (42.2 g), 20% KOH aqueous solution (63.8 g), and trioctylmethylammonium chloride (1.5 g) were added to a eggplant-shaped flask, cooled in an ice bath, and carbon disulfide (15.9 g) was added. ) And tetrahydrofuran (hereinafter, also referred to as "THF") (38 ml) were added, and the mixture was stirred for 20 minutes. A THF solution (170 ml) of α, α'-dichloro-p-xylene (16.6 g) was added dropwise over 30 minutes. After reacting at room temperature for 1 hour, the mixture was extracted from chloroform, washed with pure water, dried over anhydrous sodium sulfate, and concentrated on a rotary evaporator. The obtained crude product is purified by column chromatography and then recrystallized from ethyl acetate to form 1,4-bis (n-dodecylsulfanylthiocarbonylsulfanylmethyl) benzene represented by the following formula (1). (Hereinafter, also referred to as “DLBTTC”) was obtained in a yield of 80%. ¹ The peak of the target product was confirmed at 7.2 ppm, 4.6 ppm, and 3.4 ppm by 1 H-NMR measurement.

Preparation Example 3 (Synthesis of 4-functional RAFT agent TLBTTC)
(Synthesis of 1,2,4,5-Tetrakis (n-dodecylsulfanylthiocarbonylsulfanylmethyl) benzene)
1-Dodecanethiol (7.2 g), 20% KOH aqueous solution (10.9 g), and trioctylmethylammonium chloride (0.13 g) were added to a eggplant-shaped flask, cooled in an ice bath, and carbon disulfide (2.7 g) was added. ), THF (57 ml) was added, and the mixture was stirred for 20 minutes. A THF solution (80 ml) of 1,2,4,5-tetra (bromomethyl) (3.6 g) was added dropwise over 30 minutes. After reacting at room temperature for 1 hour, the mixture was extracted from chloroform, washed with pure water, dried over anhydrous sodium sulfate, and concentrated on a rotary evaporator. The obtained crude product is purified by column chromatography and then recrystallized from hexane to form 1,2,4,5-tetrakis (n-dodecylsulfanylthiocarbonylsulfanyl) represented by the following formula (2). Methyl) benzene (hereinafter also referred to as "TLBTTC") was obtained in a yield of 88%. ¹ The peak of the target product was confirmed at 7.2 ppm, 4.6 ppm, and 3.4 ppm by 1 H-NMR measurement.

(2) Synthesis of polymer (RAFT polymerization)
Synthesis Example 1 (Production of Polymer A)
DLBTTC (4.2 g), 2,2'-azobis (2-methylbutyronitrile) (hereinafter also referred to as "ABN-E") (0.25 g), butyl acrylate in a 1 L flask equipped with a stirrer and a thermometer. (Hereinafter referred to as "BA") (307.0 g), ethyl acrylate (hereinafter also referred to as "EA") (20.5 g), tetradecyl acrylate (hereinafter also referred to as "TDA") (82.0 g), methyldimethoxy Cyrilpropyl methacrylate (0.6 g) and anisole (276.4 g) were charged, sufficiently degassed by nitrogen bubbling, and polymerization was started in a constant temperature bath at 60 ° C. After 4 hours, the reaction was stopped by cooling to room temperature. The above polymerization solution was reprecipitated and purified from methanol and vacuum dried to obtain a polymer A. The molecular weight of the obtained polymer A was Mn43,200, Mw49,300, and Mw / Mn1.14 as measured by GPC (gel permeation chromatography) (in terms of polystyrene). The number of crosslinkable silyl groups in the main chain per molecule of polymer A, calculated from the amount of methyldimethoxysilylpropyl methacrylate introduced and Mn, was 0.4.

Synthesis Examples 2 to 7, Comparative Synthesis Examples 1 to 3 (Synthesis of Polymers B to J)
Polymers B to J were obtained in the same manner as in Synthesis Example 1 except that the amount of the monomer used, the type and amount of the RAFT agent used, and the amount of the solvent used were changed as shown in Table 2. .. Table 2 shows the molecular weight of each polymer and the number of crosslinkable silyl groups in the main chain per molecule.

The abbreviations in Table 2 mean the following.
-BA: n-butyl acrylate-EA: ethyl acrylate-TDA: tetradecyl acrylate-DLBTTC: 1,4-bis (n-dodecylsulfanylthiocarbonylsulfanylmethyl) benzene-TLBTTC: 1,2,4,5- Tetrax (n-dodecylsulfanylthiocarbonylsulfanylmethyl) benzene-ABN-E: 2,2'-azobis (2-methylbutyronitrile)

(3) Dethiocarbonyl group and polymer terminal functionalization
Production Example 1 (Production of Polymer 1)
The polymer A (100 parts) and anisole (100 parts) obtained in Synthesis Example 1 were charged into a 500 ml flask equipped with a stirrer and a thermometer, and heated to 40 ° C. in a constant temperature bath to sufficiently dissolve the polymer A. After adding n-propylamine (1.4 parts) to this solution and stirring for 30 minutes, a part of the solution was withdrawn, and this solution was reprecipitated and purified from methanol and vacuum dried. ^{1 From 1} H-NMR measurement, the proton-derived peak (4.9 ppm) on the carbon to which the RAFT group is bonded disappears almost completely, and instead the proton-derived peak (4.9 ppm) on the carbon to which the SH group is bonded disappears. 3.4 ppm) appeared. From this peak integral value and the peak integral value derived from the benzene ring at the starting end, it was confirmed that the number of SH groups per molecule was 2.0.
Then, KBM-5103 (10.8 parts) was added, and the reaction was carried out for 5 hours. The obtained solution was reprecipitated and purified from methanol and vacuum dried to obtain Polymer 1.
The molecular weight of the obtained polymer 1 was Mn43,500, Mw49,800, and Mw / Mn1.14 as measured by GPC (gel permeation chromatography) measurement (in terms of polystyrene). ^{1 From 1} H-NMR measurement, it was confirmed that the proton-derived peak (3.4 ppm) on the carbon to which the SH group was bonded disappeared almost completely. That is, since the number of crosslinkable silyl groups at the terminal of the polymer 1 is 2.0, the number of crosslinkable silyl groups per molecule of the polymer 1 is 2.4.

Production Examples 2-9, Comparative Production Examples 1-2 (Production of Polymers 2-11)
The same operation as in Production Example 1 was carried out except that the type of polymer, the amount of nucleophile used, and the type and amount of reactant used were changed as shown in Table 3, to obtain polymers 2 to 11. .. Table 3 shows the molecular weight of each polymer, the number of crosslinkable silyl groups at the terminal of the polymer, and the number of crosslinkable silyl groups per polymer molecule.

The abbreviations in Table 3 mean the following.
KBM-5103: 3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.
Shinetsu Silicone "KBM-5103"
-KBE-403: 3-glycidoxypropyltriethoxysilane, Shin-Etsu Silicone "KBE-403" manufactured by Shin-Etsu Chemical Co., Ltd.
KBE-9007N: 3-Isocyanate Propyltriethoxysilane, Shin-Etsu Chemical
Shinetsu Silicone Co., Ltd. "KBE-9007N"

(4) Preparation and evaluation of curable resin composition
Example 1
Using the polymer 1 obtained in Production Example 1 as the base resin, curable resin compositions (formulation A and formulation B) were prepared according to the above-mentioned formulation table (Table 1), and each was a cured sheet (cured product). Was produced. The tensile physical characteristics of the cured sheet obtained from Formulation A and Formulation B were evaluated, respectively. In addition, the weather resistance of the cured sheet obtained from Formulation B was evaluated. The results are shown in Table 4.

Examples 2-9, Comparative Examples 1-3
The polymers 2-9 obtained in Production Examples 2-9, the polymers 10 and 11 obtained in Comparative Production Examples 1 and 2, and the polymer J obtained in Comparative Synthesis Example 3 were used as described above. A curable resin composition (formulation A and formulation B) was prepared according to the formulation table (Table 1), and a cured sheet (cured product) was prepared. The tensile physical characteristics of the cured sheet obtained from Formulation A and Formulation B were evaluated, respectively. In addition, the weather resistance of the cured sheet obtained from Formulation B was evaluated. The results are shown in Table 4.

<Evaluation result>
As is clear from the results of Examples 1 to 9, the cured sheet obtained from the curable resin composition of the present invention exhibits good tensile physical characteristics (breaking elongation and breaking strength), is excellent in toughness, and has weather resistance. It was also excellent. Among these, focusing on the number of crosslinkable silyl groups in the main chain per molecule of the polymer, the larger the number, the better the weather resistance (Examples 1 to 6), and it is particularly suitable for use as a sealing material.
On the other hand, when the main chain of the vinyl polymer does not have a structural unit derived from a monomer containing a crosslinkable functional group (Comparative Examples 1 and 2), or when the terminal of the vinyl polymer is crosslinked. In the case of having no sex functional group (Comparative Example 3), the result was that at least toughness or weather resistance was inferior as compared with Examples.

Claims (13)

A curable resin composition containing a vinyl-based polymer having a crosslinkable functional group, wherein the vinyl-based polymer has two or more ends and is crosslinkable to the main chain of the vinyl-based polymer and the ends. A curable resin composition having a functional group. The curable resin composition according to claim 1, wherein the average number of crosslinkable functional groups per molecule of the vinyl polymer is 2 to 30. The curable resin composition according to claim 1 or 2, wherein the average number of crosslinkable functional groups in the main chain per molecule of the vinyl polymer is 0.2 to 20. The curable resin composition according to any one of claims 1 to 3, wherein the average number of terminal crosslinkable functional groups per molecule of the vinyl polymer is 0.4 to 12. The crosslinkable functional group is one selected from the group consisting of an epoxy group, a hydroxyl group, a formyl group, a carboxyl group, a sulfonic acid group, an isocyanato group, a crosslinkable silyl group, an amino group, and a (meth) acryloyl group. The curable resin composition according to any one of claims 1 to 4. The vinyl-based polymer has the formula (5):

(During the ceremony,
R represents an n-valent organic group which may have one or more heteroatoms selected from the group consisting of oxygen atoms, nitrogen atoms and sulfur atoms.
n represents an integer of 2 or more.
U and W are the same or different, respectively, -CO ₂ H, -CO ₂ R ¹ , -C (= O) R ¹ , -C (= S) R ¹ , -C (= S) OR ¹ ,- C (= O) SR ¹ , -C (= O) NH ₂ , -C (= O) NHR ¹ , -C (= O) N (R ¹ ) ₂ , with hydrogen atom, halogen atom, or substituent Indicates an alkyl group which may be used. Alternatively, U and W may be bonded to each other to form a ring with adjacent carbon atoms to which they are bonded, and the ring may have a substituent.
V is the same or different, hydrogen atom, R ¹ , -CO ₂ H, -CO ₂ R ¹ , -C (= O) R ¹ , -C (= S) R ¹ , -C (= S) OR ¹ , -C (= O) SR ¹ , -C (= O) NH ₂ , -C (= O) NHR ¹ , -C (= O) N (R ¹ ) ₂ , -OR ¹ , -SR ¹ , It indicates -OC (= O) R ¹ , -SC (= O) R ¹ , or -OC (= S) R ^1.
R ¹ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a cycloalkyl group, a heterocycloalkyl group, an aralkyl group, a heteroarylalkyl group, or a polymer chain, and these groups or chains are substituted. It may have a group. If R ¹ is plurally present, they may be the same or different.
k represents an integer of 2 or more.
Here, at least one group selected from the group consisting of U, V, and W contains a crosslinkable functional group.
X represents a group or a hydrogen atom containing a crosslinkable functional group, which is the same or different. All or part of X is a group containing a crosslinkable functional group. )
The curable resin composition according to any one of claims 1 to 5, which is a compound represented by. The crosslinkable functional group contained in at least one group selected from the group consisting of U, V, and W and the crosslinkable functional group contained in the group represented by X are the same or different, epoxy. The curable resin composition according to claim 6, which is a group, a hydroxyl group, a formyl group, a carboxyl group, a sulfonic acid group, an isocyanato group, a crosslinkable silyl group, an amino group, or a (meth) acryloyl group. The claim that the crosslinkable functional group contained in at least one group selected from the group consisting of U, V, and W and the crosslinkable functional group contained in the group represented by X are the same. The curable resin composition according to 6 or 7. The curable resin composition according to any one of claims 1 to 8, wherein the vinyl-based polymer has a molecular weight distribution (Mw / Mn) of less than 2.0. The curable resin composition according to any one of claims 1 to 9, wherein the crosslinkable functional group is a crosslinkable silyl group. The curable resin composition according to any one of claims 1 to 10, further comprising a polyoxyalkylene polymer having a crosslinkable silyl group. The curable resin composition according to any one of claims 1 to 11, which is applied as a sealing material application. A cured product of the curable resin composition according to any one of claims 1 to 12.