JP6798188B2 - Block copolymer, its production method, and curable resin composition - Google Patents

Description

The present invention relates to block copolymers, methods for producing them, and curable resin compositions.

The curable resin composition containing a polymer having a crosslinkable silyl group is filled between interior and exterior members of a building and joints of joints to prevent the invasion of wind and rain, and various base materials. It is used as an adhesive to bond. In particular, a curable resin composition containing a polymer having a crosslinkable silyl group whose main chain structure is an oxyalkylene polymer has been used as a building sealant and an adhesive for adhering various base materials for more than 30 years. Has been done. Further, in recent years, curable resin compositions containing a crosslinkable silyl group-containing vinyl polymer have been widely used as a highly weather-resistant sealing material due to the good weather resistance due to the main chain structure in the trend of extending the life of houses. It has come to be used.

An oxyalkylene polymer having at least one crosslinkable silyl group is excellent in flexibility, coating property, and stain resistance, but in particular, polyoxyalkylene having a polypropylene oxide as a main chain is easily deteriorated by heat and ultraviolet rays. , There is a problem that the weather resistance of the cured product deteriorates. In order to solve this problem, a curable resin composition having improved weather resistance by blending an oxyalkylene polymer having at least one crosslinkable silyl group with an acrylic polymer having at least one crosslinkable silyl group. Things have been proposed.

For example, Patent Document 1 describes a (meth) acrylic polymer having at least one specific crosslinkable silyl group as a component, a thickener which is a carboxylic acid ester having no aromatic, a plasticizer, and a specific one. A curable resin composition containing a polyether polymer having at least one crosslinkable silyl group is described (claim 10).

JP-A-2010-138394

However, as examined by the present inventor, in the blend of the oxyalkylene polymer having at least one crosslinkable silyl group and the (meth) acrylic polymer having at least one crosslinkable silyl group, the (meth) acrylic type is used. Depending on the content of the polymer, the viscosity of the polymer mixture may be high, which may impair workability or reduce the tensile properties such as breaking strength and breaking elongation inherent in the oxyalkylene polymer. It became clear that it was difficult to achieve both properties and tensile properties after curing.

Therefore, in the present invention, a block copolymer for obtaining a curable resin composition having excellent workability and good tensile properties after curing, a method for producing the block copolymer, and a curable resin composition containing the block copolymer. The challenge is to provide goods.

As a result of diligent studies to solve the above problems, the present inventor has a specific formula of an oxyalkylene polymer block (A) and an organic polymer block (B) other than the oxyalkylene polymer block (A). The oxyalkylene polymer block (A) and the organic polymer block (B) are bonded by the bonding unit (X), and are represented by a specific formula. According to the block copolymer having at least one crosslinkable silyl group (C), it was found that a curable resin composition having excellent workability and good tensile properties after curing can be obtained. The present invention has been completed.

That is, the present invention is the following [1] to [8].
[1] An oxyalkylene polymer block (A), an organic polymer block (B) other than the oxyalkylene polymer block (A), and a bonding unit (X) represented by the following formula (2) are attached. Including
The oxyalkylene polymer block (A) and the organic polymer block (B) are bonded by the bonding unit (X), and
A block copolymer having at least one crosslinkable silyl group (C) represented by the following formula (1).
The block copolymer is a block copolymer that does not contain urethane bonds.
-[Si (R ¹ ) _2-b (Y) _b O] _{m -} Si (R ² ) _3-a (Y) _a (1)
In the formula (1), R ¹ and R ² are independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R') _3. represents a triorganosiloxy group represented by SiO-, when R ¹ is present two or more, they may be the same or different and when R ² is present two or more, they It may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they may be the same and different, and R'is the number of carbon atoms. It represents 1 to 20 monovalent hydrocarbon groups, and the three R's may be the same or different from each other. a is 0, 1, 2, or 3, b is 0, 1, or 2, and m is an integer from 0 to 19. However, 1, b and m satisfy a + mb ≧ 1.
-[Si (R ¹¹ ) (R ¹² ) O] _n- Si (R ¹³ ) (R ¹⁴ )-(2)
In formula (2), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, respectively. represents a group, when R ¹¹ is present two or more, they may be the same or different and when R ¹² is present two or more, even if they have be the same or different Often, n is an integer greater than or equal to 1.
[2] The block copolymer according to the above [1], wherein the organic polymer block (B) is a vinyl-based polymer block.
[3] The block copolymer according to the above [1] or [2], wherein the polystyrene-equivalent number average molecular weight is 8000 to 50000.
[4] The ratio of the total number of moles of the repeating units of the oxyalkylene polymer block (A) to the total number of moles of the repeating units of the organic polymer block (B) is 10:90 to 90:10. 1] The block copolymer according to any one of [3].
[5] A curable resin composition containing the block copolymer according to any one of the above [1] to [4].
[6] The curable resin composition according to the above [5], which further contains calcium carbonate and a curing catalyst.
[7] The curable resin composition according to the above [6], wherein the curing catalyst is a divalent tin compound or a tetravalent tin compound.
[8] An oxyalkylene polymer (D) having an alkenyl group at the terminal and not containing a urethane bond, and an oxyalkylene polymer having an alkenyl group at the terminal and not containing a urethane bond, other than the oxyalkylene polymer. The organic polymer (E) and the compound (X') represented by the following formula (2') are bonded by a hydrosilylation reaction to synthesize a block copolymer (F) having an alkenyl group at the terminal. Process and
A step of synthesizing a block copolymer having a crosslinkable silyl group by adding a compound (C') represented by the following formula (1') to the block copolymer (F).
A method for producing a block copolymer.
H- [Si (R ¹ ) _2-b (Y) _b O] _{m -} Si (R ² ) _3-a (Y) _a (1')
In formula (1'), R ¹ and R ² are independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R'). represents a triorganosiloxy group represented by ₃ SiO-, when R ¹ is present two or more, they may be the same or different and when R ² is present two or more, they May be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they may be the same and different, and R'is carbon. It represents a monovalent hydrocarbon group of numbers 1 to 20, and the three R's may be the same or different from each other. a is 0, 1, 2, or 3, b is 0, 1, or 2, and m is an integer from 0 to 19. However, 1, b and m satisfy a + mb ≧ 1.
H- [Si (R ¹¹ ) (R ¹² ) O] _n- Si (R ¹³ ) (R ¹⁴ ) -H (2')
In formula (2'), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ independently have an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 7 to 20 carbon atoms, respectively. an aralkyl group, when R ¹¹ is present two or more, they may be the same or different and when R ¹² is present two or more, they have be the same or different Also, n is an integer of 1 or more.

According to the present invention, a block copolymer for obtaining a curable resin composition having excellent workability and good tensile properties after curing, a method for producing the block copolymer, and a curable resin composition containing the block copolymer. Can provide things.

The block copolymer of the present invention, a method for producing the block copolymer, and a curable resin composition will be described below.
The numerical range represented by using "~" in the present specification means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
Further, in the present specification, "(meth) acrylic" means "acrylic and / or methacrylic".

[Block copolymer]
The block copolymer of the present invention comprises an oxyalkylene polymer block (A), an organic polymer block (B) other than the oxyalkylene polymer block, and a bonding unit (X) represented by a specific formula. The oxyalkylene polymer block (A) and the organic polymer block (B) are bonded by the bonding unit (X) and have at least one specific crosslinkable silyl group (C), and are urethane. It is a block copolymer containing no bond.

Since the block copolymer of the present invention has such a structure, it is considered that a curable resin composition having excellent workability and good tensile properties after curing can be obtained.
As described above, the block copolymer of the present invention includes an oxyalkylene polymer block (A) and an organic polymer block (B) other than the oxyalkylene polymer block (A).
The curable resin composition by blending the oxyalkylene polymer (A') corresponding to the oxyalkylene polymer block (A) and the organic polymer (B') corresponding to the organic polymer block (B) is working. Although the properties and tensile properties after curing are not sufficient, workability and after curing can be achieved by using a block copolymer containing an oxyalkylene polymer block (A) and an organic polymer block (B). The tensile properties of the polymer are improved and become sufficient.

The reason for this is not clear, but it is presumed to be as follows.
The blend of the oxyalkylene polymer (A') and the organic polymer (B') does not have sufficient compatibility at least on a micro scale, and the oxyalkylene polymer (A) and the organic polymer (B) As a result of the variation in the intermolecular interaction, it is considered that workability and tensile properties after curing could not be compatible on a macro scale.
On the other hand, in the present invention, instead of the blend of the oxyalkylene polymer (A') and the organic polymer (B'), the oxyalkylene polymer block (A) and the organic polymer block (B) are used. By using a block copolymer bonded via a bonding unit (X), compatibility on a microscopic scale can be made sufficient, and workability and tensile properties after curing can be improved on a macroscopic scale. It is probable that they were able to achieve both.

The ratio of the total number of moles of the repeating units of the oxyalkylene polymer block (A) to the total number of moles of the repeating units of the organic polymer block (B) per molecule of the block copolymer of the present invention is not particularly limited. It is preferably 10:90 to 90:10, more preferably 20:80 to 80:30, and even more preferably 30:70 to 70:30.
When the ratio of the total number of moles of the repeating units is within this range, the balance between the effect derived from the oxyalkylene polymer block (A) and the effect derived from the organic polymer block (B) becomes more excellent.

The molecular weight of the block copolymer of the present invention is not particularly limited, but the polystyrene-equivalent number average molecular weight is preferably 8000 to 50000, more preferably 1000 to 40,000, and further preferably 16000 to 32000.
When the molecular weight is within this range, the balance between workability and tensile properties after curing becomes better.

The molecular weight of the block copolymer of the present invention is a number average molecular weight (in terms of polystyrene) measured by gel permeation chromatography (GPC), and is measured in tetrahydrofuran (THF), N, N-. It is preferable to use dimethylformamide (DMF) as a mobile phase (eluent, solvent).

<Oxyalkylene polymer block (A)>
The oxyalkylene polymer block (A) is not particularly limited as long as it is an organic polymer block containing an alkylene oxide as a monomer unit, and other conditions are not particularly limited.
The oxyalkylene polymer block (A) is preferably a polypropylene oxide-based polymer block whose main chain is essentially polypropylene oxide, and more preferably a polypropylene oxide block whose main chain is polypropylene oxide.
Here, "the main chain is essentially polypropylene oxide" means that the propylene oxide unit is preferably 50% or more, more preferably 70% or more, still more preferably 90% of the repeating units constituting the main chain. It means to occupy the above.

The molecular weight of the polyoxyalkylene polymer block (A) is not particularly limited, but usually depends on how the oxyalkylene polymer block (A) is introduced into the block copolymer of the present invention, or according to the present invention. The preferred range varies depending on the average number of blocks of the oxyalkylene polymer (A) per molecule of the block copolymer.
For example, when the block copolymer of the present invention contains an oxyalkylene polymer block (A) of n _A blocks (n _A represents a real number of 1 or more) on average per molecule, the n _A block The total molecular weight of the oxyalkylene polymer block (A) is not particularly limited, but is preferably 4000 to 25000, more preferably 5000 to 20000, and even more preferably 800 to 16000.
When the total molecular weight of the oxyalkylene polymer block (A) per molecule of the block copolymer of the present invention is within this range, the workability of the curable resin composition and the tensile properties after curing are improved. Can be.

The molecular weight of the oxyalkylene polymer block (A) is represented by the number average molecular weight of the corresponding oxyalkylene polymer (A').
Here, the number average molecular weight is the number average molecular weight (polystyrene equivalent) measured by gel permeation chromatography (GPC), and is measured in tetrahydrofuran (THF), N, N-dimethylformamide (DMF). Is preferably used as the mobile phase (eluent, solvent).

The molecular weight distribution of the oxyalkylene polymer (A'), that is, the ratio (Mw / Mn) of the mass average molecular weight (Mw) to the number average molecular weight (Mn) is not particularly limited, but is preferably narrow and specifically. Is preferably less than 1.8, more preferably 1.7 or less, still more preferably 1.6 or less, even more preferably 1.5 or less, even more preferably 1.4 or less, and particularly preferably 1.3 or less. is there. By setting the range to such a narrow range, it becomes easy to suppress the viscosity of the block copolymer of the present invention as a curable resin composition to a low level, improve workability, and obtain sufficient tensile properties. .. The molecular weight distribution is most commonly measured by gel permeation chromatography (GPC). Chloroform or THF is used as the mobile phase, and a polystyrene gel column is used as the column.

<Organic polymer block (B)>
The organic polymer block (B) is not particularly limited as long as it is an organic polymer block other than the oxyalkylene polymer block (A).
Examples of the organic polymer block (B) include vinyl-based polymer blocks, polyester-based polymer blocks, polycarbonate-based polymer blocks, polyolefin-based polymer blocks, polyisobutylene-based polymer blocks, and polybutadiene-based polymer blocks. Can be selected according to the desired function.
The organic polymer block (B) is preferably a vinyl-based polymer block (B1) because the flexibility of the cured product becomes better by selecting an appropriate monomer.

The monomer constituting the main chain of the vinyl polymer block (B1) is not particularly limited as long as it is a vinyl monomer.
Specific examples of the vinyl-based monomer include (meth) acrylic acid, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, and isopropyl (meth) acrylic acid. N-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, N-Heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth) ) Phenyl acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ( Of 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, (meth) acrylate Ethylene oxide adduct, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate- 2-Perfluorobutylethyl, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2 (meth) acrylate -(Meta) acrylic acids such as perfluoroethylmethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, and 2-perfluorohexadecylethyl (meth) acrylate. System monomers: styrene-based monomers such as styrene, vinyl toluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; Fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; vinyltrimethoxy Silicon-containing vinyl monomers such as silane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid , Monoalkyl and dialkyl esters of fumaric acid; Maleimide-based monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; , And nitrile group-containing vinyl monomers such as methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl acetates, vinyl propionates, vinyl pivalates, vinyl benzoate, and vinyl silicates. Esters; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; and vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like.
The vinyl-based monomer may be used alone or in combination of two or more.

The vinyl polymer block (B1) is preferably an acrylic polymer block in which the main chain is essentially poly (n-butyl acrylate) or poly (2-ethylhexyl acrylate) in terms of physical properties. , More preferably an acrylic polymer block having a poly (n-butyl acrylate) main chain.
Here, "the main chain is essentially poly (n-butyl acrylate)" or "the main chain is essentially poly (2-ethylhexyl acrylate)" means n-butyl acrylate units or acrylic. It means that the 2-ethylhexyl acid unit occupies preferably 50% or more, more preferably 70% or more, still more preferably 90% or more of the repeating units constituting the main chain.

The molecular weight of the organic polymer block (B) is not particularly limited, but usually depends on how the organic polymer block (B) is introduced into the block copolymer of the present invention, or the block copolymer weight of the present invention. The suitable range varies depending on the average number of blocks of the organic polymer block (B) per molecule of the coalescence.
For example, when the block copolymer of the present invention contains an organic polymer block (B) of n _B blocks (n _B represents a real number of 1 or more) on average per molecule, the organic of n _B blocks The total molecular weight of the polymer block (B) is not particularly limited, but is preferably 4000 to 25000, more preferably 5000 to 20000, and even more preferably 800 to 16000.
When the total molecular weight of the organic polymer block (B) per molecule of the block copolymer of the present invention is within this range, the workability of the curable resin composition and the tensile properties after curing are improved. Can be.

The molecular weight of the organic polymer block (B) is represented by the number average molecular weight of the corresponding organic polymer (B').
Here, the number average molecular weight is the number average molecular weight (polystyrene equivalent) measured by gel permeation chromatography (GPC), and is measured in tetrahydrofuran (THF), N, N-dimethylformamide (DMF). Is preferably used as the mobile phase (eluent, solvent).

The molecular weight distribution of the organic polymer (B'), that is, the ratio (Mw / Mn) of the mass average molecular weight (Mw) to the number average molecular weight (Mn) is not particularly limited, but is preferably narrow, and specifically. It is preferably less than 1.8, more preferably 1.7 or less, still more preferably 1.6 or less, even more preferably 1.5 or less, even more preferably 1.4 or less, and particularly preferably 1.3 or less. .. By setting the range to such a narrow range, it becomes easy to suppress the viscosity of the block copolymer of the present invention as a curable resin composition to a low level, improve workability, and obtain sufficient tensile properties. .. The molecular weight distribution is most commonly measured by gel permeation chromatography (GPC). Chloroform or THF is used as the mobile phase, and a polystyrene gel column is used as the column.

<Crosslinkable silyl group (C)>
The crosslinkable silyl group (C) is represented by the following formula (1).
[-Si (R ¹ ) _2-b (Y) _b O] _m- Si (R ² ) _3-a (Y) _a (1)

In the above formula (1), R ¹ and R ² are independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R'). represents a triorganosiloxy group represented by ₃ SiO-, when R ¹ is present two or more, they may be the same or different and when R ² is present two or more, they May be the same or different. R'represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R's may be the same as or different from each other.

In the above formula (1), Y represents a hydroxyl group or a hydrolyzable group, and when two or more Ys are present, they may be the same or different. The total sum of Y is preferably in the range of 1 to 5.

The hydrolyzable group is not particularly limited, and examples thereof include hydrogen, halogen atom, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, aminooxy group, mercapto group and alkenyloxy group. Of these, an alkoxy group is preferable because it has mild hydrolyzability and is easy to handle.

In the above equation (1), a is 0, 1, 2 or 3, b is 0, 1 or 2, and m is an integer. Y can be bonded to one silicon atom in the range of 1 to 3. a, b and m satisfy a + mb ≧ 1. That is, at least one Y is included in the above formula (1).

One silicon atom constituting the crosslinkable silyl group may be present, or two or more silicon atoms may be present. In the case of silicon atoms linked by a siloxane bond, the number may be up to about 20, so m is preferably 0 to 19.

<Joining unit (X)>
The joining unit (X) is represented by the following formula (2).
-[Si (R ¹¹ ) (R ¹² ) O] _n- Si (R ¹³ ) (R ¹⁴ )-(2)
In formula (2), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, respectively. represents a group, when R ¹¹ is present two or more, they may be the same or different and when R ¹² is present two or more, even if they have be the same or different Often, n is an integer greater than or equal to 1.

Specifically, as the joining unit (X), for example,
-Si (CH ₃ ) _2- O-Si (CH ₃ ) _2- (n = 1, R ¹¹ = R ¹² = R ¹³ = R ¹⁴ = CH ₃ ),
-Si (CH ₃ ) _2- O-Si (CH ₃ ) _2- O-Si (CH ₃ ) _2- (n = 2, R ¹¹ = R ¹² = R ¹³ = R ¹⁴ = CH ₃ ), and -Si (CH ₃ ) _2- O-Si (CH ₃ ) _2- O-Si (CH ₃ ) _2- O-Si (CH ₃ ) _2- (n = 3, R ¹¹ = R ¹² = R ¹³ = R ¹⁴ = CH ₃ )
And so on.

[Manufacturing method of block copolymer]
The method for producing the block copolymer of the present invention is not particularly limited, but for example, the oxyalkylene polymer (A') corresponding to the oxyalkylene polymer block (A) and the organic corresponding to the organic polymer block (B) are organic. The polymer (B') is synthesized and reacted with the compound (X') corresponding to the bonding unit (X), and the oxyalkylene polymer block (A) and the organic polymer block (B) are combined with the bonding unit (X'). A method of synthesizing a block copolymer bonded by X) and then reacting with a compound (C') containing a crosslinkable silyl group (C) to introduce a crosslinkable silyl group (C) (“Synthesis Method 1). ".) Can be mentioned.

<< Synthesis method 1 >>
The synthesis method 1 will be described.
An oxyalkylene polymer (A') corresponding to the oxyalkylene polymer block (A) and an organic polymer (B') corresponding to the organic polymer block (B) are synthesized.
Next, the oxyalkylene polymer (D) in which a compound having an alkenyl group is bonded to the main chain terminal of the oxyalkylene polymer (A') and the organic polymer (B') and the alkenyl group is bonded to the carbon atom at the terminal. And the organic polymer (E) is synthesized.
Next, the oxyalkylene polymer (D) and the organic polymer (E) and the compound (X') represented by the following formula (2') are bonded by a hydrosilylation reaction to form an alkenyl group at the terminal of the main chain. The block copolymer (F) having the above is synthesized.
Next, the block copolymer (F) synthesized is subjected to an addition reaction with the silane compound (C') represented by the above formula (1') used in the above-mentioned synthesis method 1 to obtain the block copolymer of the present invention. Can be synthesized.

-[Si (R ¹¹ ) (R ¹² ) O] _n- Si (R ¹³ ) (R ¹⁴ )-(2)
In formula (2), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, respectively. represents a group, when R ¹¹ is present two or more, they may be the same or different and when R ¹² is present two or more, even if they have be the same or different Often, n is an integer greater than or equal to 1.

<< Method for synthesizing oxyalkylene polymer (A') >>
The method for producing the oxyalkylene polymer is not particularly limited and may be a conventionally known method. Examples thereof include the production methods described in JP-A-50-156599, JP-A-55-125121 and the like. Be done.

<< Method for synthesizing organic polymer (B') >>
The method for synthesizing the organic polymer (B') corresponding to the organic polymer block (B) is not particularly limited, and various methods can be used.

When the organic polymer block (B) is a vinyl polymer block (B1), the synthesis of the vinyl polymer corresponding to the vinyl polymer block (B1) has the versatility of the monomer and the ease of control. From the point of view, it is preferable to carry out by the radical polymerization method.

The radical polymerization method is radical polymerization in which the polymerization rate is high and the termination reaction due to coupling between radicals is likely to occur, so that it is difficult to control. However, the termination reaction is difficult to occur and the molecular weight distribution is narrow (Mw / Mn). The living radical polymerization method is preferable because a polymer can be obtained and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

In a narrow sense, living polymerization refers to polymerization in which the terminal is always active and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. It also includes pseudo-living polymerization that grows while in equilibrium. The definition in the present invention is also the latter.

[Curable resin composition]
The curable resin composition of the present invention contains the block copolymer of the present invention.
<Block copolymer>
The block copolymer of the present invention is as described above.

Since the curable resin composition of the present invention has the effects of improving the breaking strength and breaking elongation of the cured product, developing the thixo property, and improving the adhesiveness, in addition to the block copolymer of the present invention, calcium carbonate And preferably contain a curing catalyst.

Examples of the calcium carbonate include heavy calcium carbonate and colloidal calcium carbonate (precipitated calcium carbonate).
The specific surface area of the calcium carbonate is not particularly limited, but is preferably 1.5 m ² / g or more and 50 m ² / g or less, more preferably 2 m ² / g or more and 50 m ² / g or less, and the specific surface area is 1.5 m. If it is less than ² / g, the improvement effect may not be sufficient. Of course, this is not the case when the viscosity is simply increased or when the purpose is only to increase the viscosity. The larger the specific surface area of calcium carbonate, the greater the effect of improving the breaking strength and breaking elongation of the cured product and the thixo property.

The specific surface area refers to a value measured by an air permeation method (a method of obtaining the specific surface area from the air permeability to a powder-filled layer) performed according to JIS K 5101 as a measurement method. As the measuring device, it is preferable to use the specific surface area measuring device SS-100 manufactured by Shimadzu Corporation.

Further, it is more preferable that the calcium carbonate is surface-treated with a surface-treating agent. It is considered that the workability of the composition of the present invention is improved when the surface-treated calcium carbonate is used as compared with the case where the surface-treated calcium carbonate is used. As the surface treatment agent, organic substances such as fatty acids, fatty acid soaps and fatty acid esters, various surfactants, and various coupling agents such as silane coupling agents and titanate coupling agents are used. Specific examples include, but are not limited to, fatty acids such as caproic acid, caprylic acid, pelargonic acid, caproic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid. And salts of those fatty acids such as sodium and potassium, and alkyl esters of those fatty acids. Specific examples of the surfactant include polyoxyethylene alkyl ether sulfate ester, long-chain alcohol sulfate ester and the like, sulfate ester type anionic surfactant such as sodium salt and potassium salt thereof, alkylbenzene sulfonic acid and alkylnaphthalene. Examples thereof include sulfonic acid, paraffin sulfonic acid, α-olefin sulfonic acid, alkylsulfone succinic acid and the like, and sulfonic acid type anionic surfactants such as sodium salt and potassium salt thereof. The treatment amount of this surface treatment agent is preferably in the range of 0.1 to 20% by mass, and more preferably in the range of 1 to 5% by mass with respect to calcium carbonate. If the treated amount is less than 0.1% by mass, the effect of improving workability may not be sufficient, and if it exceeds 20% by mass, the storage stability of the curable composition is lowered or the cured product is deteriorated. Breaking strength and breaking elongation may decrease.

Although not particularly limited, the combination of heavy calcium carbonate and colloidal calcium carbonate can be expected to moderately suppress an increase in the viscosity of the formulation and greatly improve the breaking strength, breaking elongation, and adhesiveness of the cured product.

The content of the calcium carbonate in the curable resin composition of the present invention is not particularly limited, but is preferably 5 to 500 parts by mass with respect to 100 parts by mass of the total amount of the block copolymer of the present invention. It is preferably 10 to 300 parts by mass, and more preferably 50 to 250 parts by mass.
When the content of the calcium carbonate is within this range, the effect of improving the breaking strength, the breaking elongation, the tix property, and the adhesiveness of the cured product is further improved, and the workability of the curable composition is improved.

《Curing catalyst》
As the curing catalyst, a known silanol condensation catalyst can be used.
For example, a tin-based curing catalyst and a curing catalyst other than the tin-based curing catalyst can be mentioned. As the curing catalyst other than the tin-based curing catalyst and the tin-based curing catalyst, only the former or the latter may be used, or both may be used in combination.

(Tin-based curing catalyst)
Specific examples of the tin-based curing catalyst include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, and dibutyltin dibutylma. Rate, dibutyltin diisooctylmalate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, and dioctyltin Dialkyltin carboxylates such as diisooctylmalate; dialkyltin oxides such as dibutyltin oxide, dioctyltin oxide, and mixtures of dibutyltin oxide and phthalates; 4 such as dialkyltin oxide or dialkyltin diacetate. Reactants of valent tin compounds with low molecular weight silicon compounds having hydrolyzable silyl groups such as tetraethoxysilane, methyltriethoxysilane, diphenyldimethoxysilane, or phenyltrimethoxysilane; tin octylate, tin naphthenate, and Divalent tin compounds such as tin stearate; monobutyltin compounds such as monobutyltin trisoctate or monobutyltin triisopropoxide; monoalkyl tins such as monooctyltin compounds; reactants of laurylamine and tin octylate And a reaction product and a mixture of an amine compound such as a mixture and an organic tin compound; a complex of dibutyltin bisacetylacetonate, dioctyltin bisacetylsettnate, dibutyltin bisethylacetonate, dioctyltin bisethylacetonate and the like. Compounds; examples thereof include tin alcoholates such as dibutyltin dimethylate, dibutyltin diethylate, dioctyltin dimethylate, and dioctyltin diethylate.
The tin-based curing catalyst may be used alone or in combination of two or more.

As the tin-based curing catalyst, a divalent tin compound or a tetravalent tin compound is preferable. These tin compounds are preferable because they have high activity as a silanol condensation catalyst. As the divalent tin compound, tin octylate or tin stearate is preferable.
As the tetravalent tin compound, a dialkyltin (IV) compound is preferable, and complex compounds such as dibutyltin bisacetylacetonate, dioctyltin bisacetylsettnate, dibutyltin bisethylacetonate, and dioctyltin bisethylacetonate are used. More preferred. Among the dialkyltin (IV) complexes, butyltin bisacetylacetonate and dibutyltin bisethylacetonate are more preferable because the final curable resin composition is less colored and easily available.
The tin-based curing catalyst may be used alone or in combination of two or more.

The content of the tin-based curing catalyst in the curable resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the block copolymer of the present invention. It is more preferably 0.2 to 10 parts by mass, and further preferably 0.5 to 5.0 parts by mass.
When the content of the tin-based curing catalyst is within this range, the curing rate is within a more preferable range, and the curing reaction is more likely to proceed sufficiently. Further, when the content of the tin-based curing catalyst is within this range, it becomes easy to obtain a good cured product having higher mechanical strength, the pot life becomes a more preferable length, and the workability is further improved. It is also preferable from.

(Curing catalysts other than tin-based curing catalysts)
Specific examples of the curing catalyst other than the tin-based curing catalyst include titanate esters such as tetrabutyl titanate and tetrapropyl titanate; aluminum trisacetylacetonate, aluminumtrisethylacetacetate, and diisopropoxy. Organic aluminum compounds such as aluminum ethyl acetoacetate; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octylate (lead 2-ethylhexanoate); butylamine, octylamine, laurylamine, di Butylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris ( Amine-based compounds such as dimethylaminomethyl) phenol, morpholin, N-methylmorpholin, and 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,5) undecene-7 (DBU); amine-based compounds Salts with carboxylic acids, etc .; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products of excess polyamines with epoxy compounds; etc., silanol condensation catalysts; and other acidic catalysts or bases. Examples thereof include known silanol condensation catalysts such as sex catalysts.
The curing catalyst other than the tin-based curing catalyst may be used alone or in combination of two or more.

The content of the curing catalyst other than the tin-based curing catalyst in the curable resin composition of the present invention is not particularly limited, but is preferably 0.1 with respect to 100 parts by mass of the total amount of the block copolymer of the present invention. It is ~ 20 parts by mass, more preferably 0.2 to 10 parts by mass, and further preferably 0.5 to 5.0 parts by mass.
When the content of the curing catalyst other than the tin-based curing catalyst is within this range, the curing rate is within a more preferable range, and the curing reaction is more likely to proceed sufficiently. Further, when the content of the curing catalyst other than the tin-based curing catalyst is within this range, it becomes easy to obtain a good cured product having higher mechanical strength, and the pot life becomes a more preferable length, so that workability is improved. It is also preferable from the viewpoint of further improvement.

"Silane coupling agent"
The curable resin composition of the present invention preferably further contains a silane coupling agent.
When the silane coupling agent is contained, the risk of the sealing material peeling from the adherend such as a siding board can be further reduced because the joint width and the like fluctuate due to an external force. Further, in some cases, it is not necessary to use a primer used for improving adhesiveness, and it is expected that the construction work will be simplified.

Specific examples of the silane coupling agent include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropylmethyldiethoxysilane, and 3-isocyanatepropylmethyldimethoxysilane. Isocyanate group-containing silane coupling agent; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl)- 3-Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-Aminopropylmethyldiethoxysilane, 3-ureidopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltrimethoxysilane, and N-vinylbenzyl-3-3 Amino group-containing silane coupling agents such as aminopropyltriethoxysilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, etc. Mercapto group-containing silane coupling agent; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Epoxy group-containing silane coupling agents such as methoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane; 2-carboxyethyltriethoxysilane, 2-carboxyethylphenylbis (2-methoxyethoxy) silane, And carboxy group-containing silane coupling agents such as N- (2-carboxymethyl) aminoethyl-3-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, and 3 -Vinyl group-containing silane coupling agent such as acroyloxypropylmethyltriethoxysilane; halogen-containing silane coupling agent such as 3-chloropropyltrimethoxysilane In addition, an isocyanurate group-containing silane coupling agent such as tris (trimethoxysilyl) isocyanurate can be mentioned.
Further, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters and the like, which are modified derivatives of these, can also be used as the silane coupling agent. it can.
The above silane coupling agent may be used alone or in combination of two or more.

The content of the silane coupling agent in the curable resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the block copolymer of the present invention. It is more preferably 0.5 to 10 parts by mass, and further preferably 2.0 to 7.0 parts by mass.
The effect of the silane coupling agent contained in the curable resin composition of the present invention is that various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, and mortar, or vinyl chloride, acrylic, etc. When used on organic substrates such as polyester, polyethylene, polypropylene, and polycarbonate, it exhibits a significant adhesive improvement effect under non-primer conditions or primer-treated conditions. When used under non-primer conditions, the effect of improving the adhesiveness to various adherends is particularly remarkable.

《Pigment》
The curable resin composition of the present invention can further contain known pigments.
When a pigment is contained, it becomes possible to make the sealant or the adhesive inconspicuous by coloring the joint or the adherend in a color close to that of the joint or the adherend. In addition, the inclusion of carbon black or titanium oxide has the effect of improving the weather resistance of the cured product.
Specific examples of the pigments include inorganic pigments such as titanium oxide, zinc oxide, ultramarine blue, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, and sulfate; azo pigments, phthalocyanine pigments, and the like. Kinacridone pigments, quinacridone quinone pigments, dioxazine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanslon pigments, flavanthron pigments, perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, quinonaphthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidezo Examples thereof include long pigments, isoindrin pigments, and organic pigments such as carbon black.

The content of the pigment in the curable resin composition of the present invention is not particularly limited, but is preferably 1 to 50 parts by mass, more preferably 1 to 50 parts by mass, based on 100 parts by mass of the total amount of the block copolymer of the present invention. Is 2 to 30 parts by mass, more preferably 5 to 10 parts by mass. When the content of the pigment is within this range, it is often possible to color the cured product without reducing the breaking strength and breaking elongation.

《Plasticizer》
The curable resin composition of the present invention preferably further contains a plasticizer.
The plasticizer is not particularly limited, and can be appropriately selected for the purpose of adjusting physical properties and / or adjusting properties. When the plasticizer is used in combination with the filler, the elongation of the obtained cured product can be increased and a large amount of the filler can be mixed, which is more advantageous.

Specific examples of the plasticizer include phthalates such as dibutylphthalate, diheptylphthalate, di (2-ethylhexyl) phthalate, diisodecylphthalate, and butylbenzylphthalate; dioctyl adipate, dioctyl sebacate, and dibutyl seva. Non-aromatic dibasic acid esters such as cate, isodecyl succinate; aliphatic esters such as butyl oleate, methyl acetyllithinolate; polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester. Esters; Phthalate esters such as tricresyl phosphate or tributyl phosphate; Trimellitic acid esters; Polysyl or polystyrenes such as poly-α-methylstyrene; Polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, And polychloroprenes; chlorinated paraffins; alkyldiphenyl and hydrocarbon oils such as partially hydrogenated phthalates; process oils; polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; Polyether-based plasticizers such as derivatives in which hydroxyl groups are converted to ester groups or ether groups; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxy stearate; sebacic acid, adipic acid, azelaic acid, or phthalic acid Polyester-based plasticizers obtained from dibasic acids such as, and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, or dipropylene glycol; various vinyl-based monomers such as acrylic plasticizers. Examples thereof include vinyl-based plasticizers obtained by polymerization by the method.
The plasticizer may be used alone or in combination of two or more.

As the plasticizer to be blended in the curable resin composition of the present invention, a polyether plasticizer and / or an acrylic plasticizer is preferable, and it is more preferable to use a polyether plasticizer and an acrylic plasticizer together.
When a polyether plasticizer and an acrylic plasticizer are added to the curable resin composition of the present invention, the viscosity and slump property of the composition, and the tensile strength and elongation of the cured product obtained by curing the composition, etc. The mechanical properties can be adjusted, and the initial physical properties can be maintained for a long period of time as compared with the case of using a low molecular weight plasticizer which is a plasticizer containing no polymer component in the molecule. Further, when the cured product is used outdoors, bleeding of the plasticizer to the surface layer is suppressed, dust and the like are less likely to adhere to the cured product, and even when a paint or the like is applied to the surface of the cured product. The softening of the coating film and the resulting stains on the coating film are less likely to occur, and the appearance can be maintained for a long period of time.

The number average molecular weight of the above-mentioned polyether plasticizer and acrylic plasticizer is not particularly limited, but is preferably 500 to 15,000, more preferably 800 to 10000, and further preferably 1000 to 8000. When the molecular weights of the polyether plasticizer and the acrylic plasticizer are within this range, the cured product can maintain the initial properties for a longer period of time, and the workability is also good.

Specific examples of the above-mentioned polyether plasticizing agent include Preminol S 1004F (number of functional groups 1; average molecular weight 3300), Preminol S 3011 (number of functional groups 3; average molecular weight 10000), Preminol PML 7021 (number of functional groups 4;) manufactured by Asahi Glass Co., Ltd. (Average molecular weight 13000), Preminol PML 3015 (3 functional groups, average molecular weight 15000), Preminol PML 7001 (3 functional groups, average molecular weight 6,000), etc., and Adecapolyether G-700 manufactured by Asahi Denka Kogyo Co., Ltd. The number of functional groups is 3, the average molecular weight is 700), and Adecapolyether G-1500 (the number of functional groups is 3, the average molecular weight is 1500) and the like.
Specific examples of the acrylic polymer include Alfon UP-1000 (average molecular weight 3000), Alfon UP-1110 (average molecular weight 2500), and Alfon UP-1170 (average molecular weight 8000) manufactured by Toa Synthetic Co., Ltd. In addition, JDX-P1000, JDX-P1010, JDX-P1020 and the like manufactured by Johnson Polymer Co., Ltd. can be mentioned.

The content of the plasticizer in the curable resin composition of the present invention is not particularly limited, but is preferably 10 to 200 parts by mass with respect to 100 parts by mass of the total amount of the block copolymer of the present invention. It is preferably 20 to 150 parts by mass, and more preferably 30 to 100 parts by mass.
When the content of the plasticizer is within this range, the flexibility of the cured product is better exhibited and the mechanical strength of the cured product is sufficient.

<< Other additives >>
Various additives may be added to the curable resin composition of the present invention, if necessary, for the purpose of adjusting various physical properties of the curable resin composition or the cured product. Examples of such additives include fillers other than calcium carbonate, thixotropic agents (anti-dripping agents), photocurable substances, antioxidants, flame retardants, curable modifiers, antioxidants, etc. Examples thereof include radical bans, metal deactivators, ozone deterioration inhibitors, phosphorus-based peroxide decomposing agents, lubricants, foaming agents and the like. These various additives may be used alone or in combination of two or more.

[Manufacturing method of curable resin composition]
The curable resin composition of the present invention may be prepared as a one-component type in which all the compounding components are compounded and sealed in advance and cured by the moisture in the air after construction, and a curing catalyst is separately added to the filler, plasticizer, etc. By blending a component such as water, it may be adjusted as a curing agent as a two-component type in which the compounding material and the polymer composition are mixed before use.
In the two-component type, a colorant can be added when the two components are mixed. For example, when providing a sealing material that matches the color of the siding board, it is possible to have abundant color assortment with a limited stock. This makes it easier to handle multicoloring, which is required by the market, and is more preferable for low-rise buildings.
As the colorant, for example, it is easy to work by using a paste obtained by mixing a pigment and a plasticizer, and in some cases, a filler. Further, the curing speed can be finely adjusted at the work site by adding a retarder when the two components are mixed.

[Use of cured product]
The curable resin composition of the present invention is not particularly limited, but is an elastic sealing material for construction, a sealing material for double glazing, an adhesive, an elastic adhesive, a coating material, a gasket, a casting material, various molding materials, and artificial marble. , And rust-proof / waterproof sealing material for wire-reinforced glass or laminated glass end face (cut part), anti-vibration / anti-vibration / sound-proof / seismic isolation materials used for automobiles, ships, home appliances, etc., automobile parts, electric appliances It can be used for various purposes such as liquid sealants used in parts and various machine parts. Among them, it can be more preferably used as an adhesive, a sealing material, or a liquid gasket.

The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.

[Synthesis Example 1]
<Synthesis of polypropylene oxide having an allyl group at the end>
To the hydroxyl group of polypropylene oxide having a number average molecular weight of 10000 (Preminol S 4012, manufactured by Asahi Glass Co., Ltd .; "Preminol" is a registered trademark), a methanol solution of sodium methoxide in an equivalent amount of 1.2 times was added to distill off methanol. The hydroxyl group was made into sodium alkoxide, and 1.2 times equivalent of allyl chloride was further added to convert the hydroxyl group into an allyloxy group.
After removing the unreacted allyl chloride, the by-produced inorganic salt is removed and purified to obtain polypropylene oxide having an allyl group at the end of the oxypropylene chain (hereinafter, may be referred to as "oxypropylene polymer (α)"). Obtained.

[Synthesis Example 2]
<Synthesis of poly (n-butyl acrylate) having an allyl group at the end>
A 1 L round-bottom flask equipped with a reflux tube was charged with cuprous bromide (2.80 g), acetonitrile (22 mL), and 1,1,4,7,7-pentamethyldiethylenetriamine (4.1 mL). , Replaced with nitrogen gas. -N-Butyl acrylate (200 g) and diethyl-2,5-dibromoadipate (7.0 g) were added, and the mixture was heated and stirred at 70 ° C. for 7 hours. The mixture was diluted with ethyl acetate and treated with activated alumina. The volatile matter was distilled off under reduced pressure to obtain 150 g of poly (-n-butyl acrylate) having halogens at both ends shown in the following formula (polymerization yield 87%). The number average molecular weight of the polymer was 10700 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.15.
1,7-Octadiene, acetonitrile (solvent), and 1,1,4,7,7-pentamethyldiethylenetriamine were added to the obtained polymer concentrate to adjust the temperature of the reaction solution to 80 to 90 ° C. While heating and stirring for several hours, octadiene was reacted at the end of the polymer. The volatile matter was removed under reduced pressure to obtain a polymer having an allyl group at the terminal.
The obtained polymer having an allyl group at the terminal is diluted with toluene to obtain a filtration aid, an adsorbent (aluminum silicate; Kyoward 700SEN, manufactured by Kyowa Chemical Industry Co., Ltd .; "Kyoward" is a registered trademark), and hydrotal. Sight (Kyoward 500SH, manufactured by Kyowa Chemical Industry Co., Ltd.) was added, heated to 80 to 100 ° C., stirred, and filtered. The filtrate was concentrated to obtain a crude polymer product.
The obtained crude polymer product contains a heat stabilizer (Sumilyzer GS, manufactured by Sumitomo Chemical Co., Ltd .; "Smilizer" is a registered trademark) and an adsorbent (Kyoward 700SEN, manufactured by Kyowa Chemical Industry Co., Ltd .; (Manufactured by Kogyo Co., Ltd.) was added, the temperature was raised while degassing under reduced pressure and stirring with heating, and the mixture was stirred under reduced pressure at 170 to 200 ° C. for several hours. It was further diluted with toluene and then filtered.
The filtrate was concentrated to obtain a poly (n-butyl acrylate) having an allyl group at the terminal (hereinafter, may be referred to as "vinyl polymer (β)").
The number average molecular weight (in terms of polystyrene) determined by GPC measurement of the obtained polymer was 10800, and the molecular weight distribution was 1.20.

[Synthesis Example 3]
<Synthesis of polypropylene oxide having a hydrolyzable silyl group at the end (1)>
To the autoclave, 0.04 g of zinc hexacyanocobalate-glime complex, 2.0 g of dipropylene glycol in THF, and 9.6 g of propylene oxide were added, and the mixture was reacted at 76 ° C. under a nitrogen atmosphere. Then 145.2 g of propylene oxide was added to the reaction system. The unreacted monomer and solvent were recovered and purified to obtain 150 g of an oily product. The obtained product showed a single peak by GPC analysis, and the molecular weight distribution (Mw / Mn) was 1.14. The hydroxyl value was 10.5 mgKOH / g.
5.2 g of a methanol solution of sodium methoxide (28% by mass) was added to 120 g of the polypropylene oxide having a hydroxyl group at the terminal obtained above, and the mixture was reacted at 130 ° C. for 1 hour in an autoclave and then volatilized under reduced pressure. The atmosphere was returned to a nitrogen atmosphere, 2.5 g of allyl chloride was added, and the mixture was reacted for 2 hours.
This reaction mixture was dissolved in hexane, adsorbed with aluminum silicate, and then distilled off under reduced pressure to obtain a polypropylene oxide having an unsaturated group (allyl group) at the terminal.
120 g of polypropylene oxide having an unsaturated group (allyl group) at the terminal obtained by the above synthesis was charged in a pressure-resistant glass reaction vessel, and a 2-propanol solution of chloroplatinic acid (25 g of H ₂ PtC _{l6.6H 2} O) was _added. After adding 0.02 g (dissolved in 500 g of 2-propanol), the mixture was stirred for 30 minutes. 1.9 g of methyldimethoxysilane was added dropwise and reacted at 90 ° C. for 2 hours. The volatile matter was removed by reducing the pressure to obtain a polypropylene oxide having a hydrolyzable silyl group at the terminal (hereinafter, may be referred to as "oxypropylene polymer (γ)").
The number average molecular weight (in terms of polystyrene) determined by GPC measurement of the obtained polymer was 19000, and the molecular weight distribution was 1.14.

[Synthesis Example 4]
<Synthesis of poly (n-butyl acrylate) having a hydrolyzable silyl group at the terminal (1)>
A 1 L three-necked round-bottom flask equipped with a reflux tube was charged with cuprous bromide (0.84 g), acetonitrile (22 mL), and 1,1,4,7,7-pentamethyldiethylenetriamine (1.2 mL). , Replaced with nitrogen gas. -N-Butyl acrylate (200 g) and diethyl-2,5-dibromoadipate (3.5 g) were added, and the mixture was heated and stirred at 70 ° C. for 7 hours. The mixture was diluted with ethyl acetate and treated with activated alumina. The volatile matter was distilled off under reduced pressure to obtain 150 g of poly (-n-butyl acrylate) having halogens at both ends shown in the following formula (polymerization yield 90%).
The number average molecular weight (in terms of polystyrene) determined by GPC measurement of the obtained polymer was 22000, and the molecular weight distribution was 1.20.
1,7-Octadiene, acetonitrile (solvent), and 1,1,4,7,7-pentamethyldiethylenetriamine were added to the obtained polymer concentrate to adjust the temperature of the reaction solution to 80 to 90 ° C. While heating and stirring for several hours, octadiene was reacted at the end of the polymer. The volatile matter was removed under reduced pressure to obtain a polymer having an allyl group at the terminal.
The obtained polymer having an allyl group at the terminal is diluted with toluene to obtain a filtration aid, an adsorbent (aluminum silicate; Kyoward 700SEN, manufactured by Kyowa Chemical Industry Co., Ltd .; "Kyoward" is a registered trademark), and hydrotal. Sight (Kyoward 500SH, manufactured by Kyowa Chemical Industry Co., Ltd.) was added, heated to 80 to 100 ° C., stirred, and filtered. The filtrate was concentrated to obtain a crude polymer product.
The obtained crude polymer product contains a heat stabilizer (Sumilyzer GS, manufactured by Sumitomo Chemical Co., Ltd .; "Smilizer" is a registered trademark) and an adsorbent (Kyoward 700SEN, manufactured by Kyowa Chemical Industry Co., Ltd .; (Manufactured by Kogyo Co., Ltd.) was added, the temperature was raised while degassing under reduced pressure and stirring with heating, and the mixture was stirred under reduced pressure at 170 to 200 ° C. for several hours. It was further diluted with toluene and then filtered. The filtrate was concentrated to obtain poly (n-butyl acrylate) having an allyl group at the terminal.
The obtained polymer had a number average molecular weight (in terms of polystyrene) of 22,500 determined by GPC measurement, and the molecular weight distribution was 1.20.
120 g of poly (n-butyl acrylate) having an unsaturated group (allyl group) at the terminal obtained by the above synthesis was charged into a pressure-resistant glass reaction vessel, and a 2-propanol solution of chloroplatinic acid (25 g of H ₂ PtC) was charged. _l6 · 6H ₂ O and those that have been dissolved in 2-propanol 500 g) after addition of 0.02 g, it was stirred for 30 minutes. 1.6 g of methyldimethoxysilane was added dropwise and reacted at 90 ° C. for 2 hours. The volatile matter was removed by reducing the pressure to obtain a poly (n-butyl acrylate) having a hydrolyzable silyl group at the terminal (hereinafter, may be referred to as "vinyl polymer (δ)").
The number average molecular weight (in terms of polystyrene) determined by GPC measurement of the obtained polymer was 23000, and the molecular weight distribution was 1.21.

[Synthesis Example 5]
<Synthesis of polypropylene oxide having a hydrolyzable silyl group at the end (2)>
120 g of polypropylene oxide having an allyl group at the terminal synthesized in Synthesis Example 1 was charged in a pressure-resistant glass reaction vessel, and a 2-propanol solution of chloroplatinic acid (25 g of H ₂ PtC _l6.6 H ₂ O was _converted into 500 g of 2-propanol. After adding 0.02 g of the dissolved product, the mixture was stirred for 30 minutes. 3.6 g of methyldimethoxysilane was added dropwise and reacted at 90 ° C. for 2 hours. The volatile matter was removed by reducing the pressure to obtain a polypropylene oxide having a hydrolyzable silyl group at the terminal (hereinafter, may be referred to as "oxypropylene polymer (ε)").
The number average molecular weight (in terms of polystyrene) determined by GPC measurement of the obtained polymer was 11000.

[Synthesis Example 6]
<Synthesis of poly (n-butyl acrylate) having a hydrolyzable silyl group at the end (2)>
120 g of poly (n-butyl acrylate) having an unsaturated group (allyl group) at the terminal obtained in Synthesis Example 2 was charged into a pressure-resistant glass reaction vessel, and a 2-propanol solution of chloroplatinic acid (25 g of H ₂ PtC) was charged. _l6 · 6H ₂ O and those that have been dissolved in 2-propanol 500 g) after addition of 0.02 g, it was stirred for 30 minutes. 3.6 g of methyldimethoxysilane was added dropwise and reacted at 90 ° C. for 2 hours. The volatile matter was removed by reducing the pressure to obtain a poly (n-butyl acrylate) having a hydrolyzable silyl group at the terminal (hereinafter sometimes referred to as "vinyl polymer (ζ)").
The number average molecular weight (in terms of polystyrene) determined by GPC measurement of the obtained polymer was 11000, and the molecular weight distribution was 1.21.

[Example 1]
<Synthesis of block copolymer 1>

After adding 100 g each of the oxypropylene polymer (α) and the vinyl-based polymer (β) to the nitrogen-substituted reaction vessel and stirring the mixture, the 1,1,3,3-tetramethyldivinylsiloxane platinum complex (VTS complex) Was added so that the amount of platinum was 2 ppm, and the mixture was stirred for 30 minutes.
Next, 0.5 equivalent of a chain extender represented by the following formula was added to the allyl group, and the mixture was reacted at 70 ° C. for 5 hours.
After the reaction, equimolar dimethoxymethylsilane was added to the chain extender, and the mixture was reacted at 70 ° C. for 5 hours.
After the reaction, the volatile matter is removed by reduced pressure to contain a polypropylene oxide block, a poly (n-butyl acrylate) block, and a bonding unit represented by the following formula for connecting the blocks, and a hydrolyzable silyl group at the terminal. A block copolymer having the above (hereinafter, may be referred to as “block copolymer 2”) was obtained.

In the bonding unit, * represents a connection point with a polypropylene oxide block or a poly (n-butyl acrylate) block.

[Comparative Examples 1 to 5]
<Preparation of curable resin composition>
Each component shown in Table 1 was blended in each blending amount to prepare a curable resin composition.

<Evaluation test>
The following evaluation test was carried out using the curable resin composition obtained as described above.

"Workability"
(viscosity)
After preparing each of the obtained curable resin compositions, the mixture was left at 23 ° C. for 1 day, and then the rotation speed was 1 rpm under the condition of 23 ° C. using a BS type viscometer (manufactured by Toki Sangyo Co., Ltd.) and No7 rotor. The viscosity was measured with.
The evaluation criteria for viscosity were as follows.
4000 Pa · s or less "○" (good)
More than 4000 Pa ・ s and less than 5000 Pa ・ s “△” (medium)
Over 5000 Pa · s "x" (bad)

(Thixotropy index)
After preparing each of the obtained curable resin compositions, the mixture was left at 23 ° C. for 1 day, and then the rotation speed was 1 rpm under the condition of 23 ° C. using a BS type viscometer (manufactured by Toki Sangyo Co., Ltd.) and No7 rotor. And 10 rpm was measured, and the obtained viscosity value was applied to the following formula to obtain the thixotropy index (TI). As shown in the following formula, TI is the ratio of the viscosity value when the rotation speed is 1 rpm to the viscosity value when the rotation speed is 10 rpm.
TI = (viscosity value when the rotation speed is 1 rpm) / (viscosity value when the rotation speed is 10 rpm)
The evaluation criteria for the thixotropy index (TI) were as follows.
TI ≧ 6.0 “○” (good)
5.5 ≤ TI <6.0 "△" (medium)
TI <5.5 "x" (bad)

《Tensile properties》
The breaking strength and breaking elongation were measured according to JIS A 1439: 2010 “Test method for building sealant”.
A primer (trade name "Primer No. 40", manufactured by Yokohama Rubber Co., Ltd.) is applied to an aluminum plate to prepare an H-type test piece, and each curable resin composition obtained is cast on the aluminum plate at 23 ° C. After curing for 7 days at 30 ° C. for 7 days, the strength at break (break strength) and the elongation at break (break elongation) of the cured product were measured at a tensile speed of 200 mm / min using an autograph manufactured by Shimadzu Corporation. A tensile test (23 ° C., 50% RH) was performed and measured.

(Breaking strength)
The evaluation criteria for breaking strength (Tb) were as follows.
Tb ≧ 0.30 MPa “○” (good)
0.20 MPa ≤ Tb <0.30 MPa "Δ" (medium)
Tb <0.20 MPa "x" (bad)

(Breaking elongation)
The evaluation criteria for elongation at break (Eb) were as follows.
Eb ≧ 300% “○” (good)
250% ≤ Eb <300% "△" (medium)
Eb <250% "x" (bad)

"Weatherability"
The curable composition was made into a sheet-like test piece having a thickness of about 3 mm and cured by curing at 23 ° C. × 3 days and 50 ° C. × 4 days, and then attached to an aluminum plate to form a metal halide weather meter (Daiprawintes). A 500-hour accelerated weather resistance test was conducted using the product.
The evaluation criteria for weather resistance were as follows.
No or few hair cracks on the surface of the test piece "○" (good)
There are many hair cracks on the surface of the test piece "x" (defective)

In Table 1, each component of the curable resin composition is as follows.
-Polymer block copolymer 1 The block copolymer 1 synthesized in Example 1
Oxypropylene polymer γ The oxypropylene polymer (γ) synthesized in Synthesis Example 3
Vinyl-based polymer δ Vinyl-based polymer (δ) synthesized in Synthesis Example 4
Oxypropylene polymer ε The oxypropylene polymer (ε) synthesized in Synthesis Example 5
Vinyl-based polymer ζ Vinyl-based polymer synthesized in Synthesis Example 6 (ζ)
・ Calcium carbonate Colloidal calcium carbonate Calfine 200M (manufactured by Maruo Calcium; "Calcine" is a registered trademark)
Surface Treatment Heavy Calcium Carbonate Lighton A-4 (manufactured by Shiraishi Calcium)
-Titanium oxide Titanium oxide (rutile type) R-820 (manufactured by Ishihara Sangyo Co., Ltd.)
-Plasticizer Acrylic polymer-based plasticizer Alfon UP-1000 (manufactured by Toagosei Co., Ltd .; "Alfon" is a registered trademark)
Polyol plasticizer Preminol PML 4002 (manufactured by Asahi Glass Co., Ltd .; "Preminol" is a registered trademark)
-Silane coupling agent Vinyl group-containing silane coupling agent KBM-1003 (manufactured by Shinetsu Silicone Co., Ltd.)
Amino group-containing silane coupling agent KBM-603 (manufactured by Shinetsu Silicone Co., Ltd.)
・ Curing catalyst Dibutyl tin Neostan U-220H (manufactured by Nitto Kasei Co., Ltd.)

As shown in Table 1, the block copolymer of Example 1 had good workability, tensile properties, and weather resistance.
On the other hand, the polymers of Comparative Examples 1 to 6 or the blends of the polymers had drawbacks in at least one of workability, tensile properties and weather resistance.
Further, from the comparison between Comparative Examples 1 and 2 and Comparative Example 3, and Comparative Examples 4 and 5 and Comparative Example 6, even if the oxypropylene polymer and the vinyl-based polymer are blended, their shortcomings cannot be compensated for. It has been suggested.

Claims (8)

The oxyalkylene polymer block (A), the organic polymer block (B) other than the oxyalkylene polymer block (A), and the bonding unit (X) represented by the following formula (2) are included.
The oxyalkylene polymer block (A) and the organic polymer block (B) are bonded by the bonding unit (X), and
A block copolymer having at least one crosslinkable silyl group (C) represented by the following formula (1).
The block copolymer does not contain urethane bonds, and is a block copolymer (excluding silicone-based block copolymers) .
-[Si (R ¹ ) _2-b (Y) _b O] _{m -} Si (R ² ) _3-a (Y) _a (1)
In the formula (1), R ¹ and R ² are independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R') _3. represents a triorganosiloxy group represented by SiO-, when R ¹ is present two or more, they may be the same or different and when R ² is present two or more, they It may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they may be the same and different, and R'is the number of carbon atoms. It represents 1 to 20 monovalent hydrocarbon groups, and the three R's may be the same or different from each other. a is 0, 1, 2, or 3, b is 0, 1, or 2, and m is an integer from 0 to 19. However, 1, b and m satisfy a + mb ≧ 1.
-[Si (R ¹¹ ) (R ¹² ) O] _n- Si (R ¹³ ) (R ¹⁴ )-(2)
In formula (2), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, respectively. represents a group, when R ¹¹ is present two or more, they may be the same or different and when R ¹² is present two or more, even if they have be the same or different Often, n is an integer greater than or equal to 1. The block copolymer according to claim 1, wherein the organic polymer block (B) is a vinyl-based polymer block. The block copolymer according to claim 1 or 2, wherein the polystyrene-equivalent number average molecular weight is 8,000 to 50,000. Claims 1 to 3 that the ratio of the total number of moles of the repeating units of the oxyalkylene polymer block (A) to the total number of moles of the repeating units of the organic polymer block (B) is 10:90 to 90:10. The block copolymer according to any one of the above items. A curable resin composition containing the block copolymer according to any one of claims 1 to 4. The curable resin composition according to claim 5, further comprising calcium carbonate and a curing catalyst. The curable resin composition according to claim 6, wherein the curing catalyst is a divalent tin compound or a tetravalent tin compound. An oxyalkylene polymer (D) having an alkenyl group at the end and not containing a urethane bond, and an organic polymer other than the oxyalkylene polymer having an alkenyl group at the end and not containing a urethane bond. A step of combining (E) with a compound (X') represented by the following formula (2') by a hydrosilylation reaction to synthesize a block copolymer (F) having an alkenyl group at the terminal.
A step of synthesizing a block copolymer having a crosslinkable silyl group by adding a compound (C') represented by the following formula (1') to the block copolymer (F).
A method for producing a block copolymer.
H- [Si (R ¹ ) _2-b (Y) _b O] _{m -} Si (R ² ) _3-a (Y) _a (1')
In formula (1'), R ¹ and R ² are independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R'). represents a triorganosiloxy group represented by ₃ SiO-, when R ¹ is present two or more, they may be the same or different and when R ² is present two or more, they May be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they may be the same and different, and R'is carbon. It represents a monovalent hydrocarbon group of numbers 1 to 20, and the three R's may be the same or different from each other. a is 0, 1, 2, or 3, b is 0, 1, or 2, and m is an integer from 0 to 19. However, 1, b and m satisfy a + mb ≧ 1.
H- [Si (R ¹¹ ) (R ¹² ) O] _n- Si (R ¹³ ) (R ¹⁴ ) -H (2')
In formula (2'), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ independently have an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 7 to 20 carbon atoms, respectively. an aralkyl group, when R ¹¹ is present two or more, they may be the same or different and when R ¹² is present two or more, they have be the same or different Also, n is an integer of 1 or more.