JP5761493B2 - Thermosetting resin material containing hyperbranched polymer having carboxyl group - Google Patents

Description

  The present invention relates to a thermosetting resin material comprising a combination of a reactive agent containing a highly branched polymer having a carboxyl group and another reactive agent containing a polyfunctional isocyanate compound. The present invention relates to a thermosetting resin material containing a highly branched polymer having an excellent carboxyl group.

Polyurethane is a polymer obtained by a thermosetting process of an isocyanate group-containing compound and a compound such as a polyol having an active hydrogen such as a hydroxy group, and since various properties can be brought out by combining these, flexible foam, rigid foam In various forms such as elastomers, adhesives, paints, and binders, they are used in a wide range of fields.
Polyurethane materials are often formulated as two-component curable compositions in order to make the properties of polyurethane after curing constant. For example, it is formulated with a polyol, catalyst and other conventional additives as the first liquid, and a polyisocyanate cross-linking agent as the second liquid, and these two liquids are usually used just before use, for example as a paint. Are mixed and used immediately before coating or the like. When the two liquids are mixed, a chemical reaction starts between the hydroxyl group of the polyol and the isocyanate group of the isocyanate compound, and finally crosslinks and cures (for example, Patent Document 1).

  Conventionally, a curing catalyst is required for the reaction between isocyanate and polyol, and organic tin compounds, carboxylic acid tin salts, carboxylic acid lead salts, and carboxylic acid bismuth salts are generally used. These compounds are economical in terms of the amount used, and are particularly excellent in terms of discoloration and other secondary effects of the resulting cured product and high catalytic activity. It is considered as a standard catalyst as a curing catalyst, and is used in a wide range of applications.

However, the curing catalysts that have been required in the past, such as lead carboxylate has a large impact on the environment, and organotin compounds are feared to affect the living body as endocrine disruptors. Necessary. In addition, since divalent tin compounds such as carboxylic acid tin salts are unstable, they have the disadvantage of being decomposed by being affected by air, moisture, or other metal ions, and also have a strong foaming reactivity and a cured product. Foamed and increased in volume and mixed with bubbles, which caused problems in the above applications.
Compared with these, the bismuth carboxylate salt is excellent in that it has less environmental toxicity and the physical properties of the cured product do not change significantly. However, because of its high activity, the pot life (time until the coating operation becomes difficult after mixing the two liquids) is relatively short, and the amount of catalyst is small due to measurement errors during preparation of the curable composition. If it fluctuates, the pot life will greatly fluctuate accordingly. When the pot life is short, the curable composition starts to gel or harden before construction, and when the pot life is long, the moldability and physical properties after execution are affected. Thus, although the bismuth carboxylate salt is excellent as a curing catalyst, it has been difficult to use due to various problems during construction.

In recent years, in particular, from the viewpoint of environmental pollution prevention and the like, processes that do not use harmful substances are required in various fields. However, in the polyurethane manufacturing site, the above-mentioned is also necessary to control the curing rate and industrial processes. There is a current situation that a catalyst must be used. Moreover, even if it is a substance with low environmental toxicity, the operability at the time of construction etc. remains a problem.
In addition, polyol compounds used in the production of conventionally used polyurethanes have strong hydrogen bonding properties due to the presence of hydroxy groups. For this reason, the resulting polyurethane has solubility and dispersibility in organic solvents, coating properties, and tertiary by curing. In some cases, further expansion or improvement of the performance range is required with respect to original curability and the like.
Polyurethane obtained by the reaction of polyol and polyisocyanate is generally used as a soft material because the polyol and polyisocyanate generally used are low-molecular-weight substances having a long chain structure, and the surface is protected. Hardness is insufficient for use as a coating material.

  The present invention has been made in view of such circumstances, and is a new curable resin material that replaces the conventional polyurethane material, that is, it has high curability even without a catalyst, and has high solubility in an organic solvent. And a curable resin material that is three-dimensionally curable.

  The inventors of the present invention have made extensive studies in order to achieve the above object, paying attention to hyperbranched polymers that have been recently developed in the course of their research, and, as a result of further research, replace the polyol component of polyurethane. Adopting a novel carboxyl group-containing hyperbranched polymer as a material and combining it with an isocyanate compound, it has excellent curability without the need for a catalyst, and has solubility in organic solvents and three-dimensional curability. The present inventors have found that a novel curable resin material can be obtained and completed the present invention.

（式［１］中、Ｒ¹は水素原子又はメチル基を表し、そしてＲ²は水素原子、カルボキシル基で置換されていてもよい炭素原子数１乃至２０のアルキル基、又はヒドロキシ基で置換されていてもよい炭素原子数１乃至２０のアルキル基を表す。）
第８観点として、前記重合開始剤Ｂが、アゾ系重合開始剤である、第１観点乃至第７観点のうち何れか一項に記載の熱硬化性樹脂材料に関する。
第９観点として、前記重合開始剤Ｂが、４，４'−アゾビス（４−シアノバレリン酸）
である、第８観点に記載の熱硬化性樹脂材料に関する。
第１０観点として、分子内に２個以上のラジカル重合性二重結合を有するモノマーＡと、該モノマーＡのモル数に対して５〜２００モル％の分子内にカルボキシル基を有する重合開始剤Ｂの存在下で重合させることにより得られる、分子末端にカルボキシル基を有する高分岐ポリマーを含む反応剤（ａ１）に関する。
第１１観点として、分子内に２個以上のラジカル重合性二重結合を有するモノマーＡと、分子内にカルボキシル基若しくはヒドロキシ基及び少なくとも１個のラジカル重合性二重結合を有するモノマーＣとを、該モノマーＡのモル数に対して５〜２００モル％の分子内にカルボキシル基を有する重合開始剤Ｂの存在下で重合させることにより得られる、分子末端にカルボキシル基を有する高分岐ポリマーを含む反応剤（ａ２）に関する。
第１２観点として、第１観点乃至第９観点のうちいずれか一項に記載の反応剤（ａ１）又は反応剤（ａ２）と反応剤（ｂ）とを混合して得られる熱硬化性樹脂組成物に関する。
第１３観点として、前記反応剤（ｂ）に含まれる多官能イソシアネート化合物のイソシアネート基のモル数に対して、前記反応剤（ａ１）又は（ａ２）に含まれる高分岐ポリマーのカルボキシル基のモル当量が０．０１〜１０である、第１２観点に記載の熱硬化性樹脂組成物に関する。
第１４観点として、第１２観点又は第１３観点に記載の熱硬化性樹脂組成物を熱硬化して得られる硬化膜に関する。
第１５観点として、分子内に２個以上のラジカル重合性二重結合を有するモノマーＡと、該モノマーＡのモル数に対して５〜２００モル％の分子内にカルボキシル基を有する重合開始剤Ｂの存在下で重合させることにより得られる、分子末端にカルボキシル基を有する高分岐ポリマーを、高められた温度で多官能イソシアネート化合物と反応せしめて硬化させることからなる、硬化樹脂の製造方法に関する。
第１６観点として、分子内に２個以上のラジカル重合性二重結合を有するモノマーＡと、分子内にカルボキシル基若しくはヒドロキシ基及び少なくとも１個のラジカル重合性二重結合を有するモノマーＣとを、該モノマーＡのモル数に対して５〜２００モル％の分子内にカルボキシル基を有する重合開始剤Ｂの存在下で重合させることにより得られる、分子末端にカルボキシル基を有する高分岐ポリマーを、高められた温度で多官能イソシアネート化合物と反応せしめて硬化させることからなる、硬化樹脂の製造方法に関する。
第１７観点として、分子内に２個以上のラジカル重合性二重結合を有するモノマーＡ（ただしジビニルベンゼンを除く）と、該モノマーＡのモル数に対して５〜２００モル％の分子内にカルボキシル基を有する重合開始剤Ｂの存在下で重合させることにより得られる、分子末端にカルボキシル基を有する高分岐ポリマーに関する。
第１８観点として、分子内に２個以上のラジカル重合性二重結合を有するモノマーＡと、分子内にカルボキシル基若しくはヒドロキシ基及び少なくとも１個のラジカル重合性二重結合を有するモノマーＣとを、該モノマーＡのモル数に対して５〜２００モル％の分子
内にカルボキシル基を有する重合開始剤Ｂの存在下で重合させることにより得られる、分子末端にカルボキシル基を有する高分岐ポリマーに関する。 That is, as a first aspect, the present invention provides a monomer A having two or more radical polymerizable double bonds in the molecule, and a carboxyl group in the molecule of 5 to 200 mol% with respect to the number of moles of the monomer A. From the combination of the reaction agent (a1) containing a highly branched polymer having a carboxyl group at the molecular end and the reaction agent (b) containing a polyfunctional isocyanate compound, obtained by polymerizing in the presence of a polymerization initiator B having The present invention relates to a thermosetting resin material.
As a second aspect, a monomer A having two or more radical polymerizable double bonds in the molecule, and a monomer C having a carboxyl group or a hydroxy group and at least one radical polymerizable double bond in the molecule, Reaction comprising a highly branched polymer having a carboxyl group at the molecular end, obtained by polymerizing in the presence of a polymerization initiator B having a carboxyl group in the molecule of 5 to 200 mol% relative to the number of moles of the monomer A The present invention relates to a thermosetting resin material comprising a combination of an agent (a2) and a reactive agent (b) containing a polyfunctional isocyanate compound.
As a 3rd viewpoint, the said monomer A is related with the thermosetting resin material as described in a 1st viewpoint or a 2nd viewpoint which is a compound which has any one or both of a vinyl group or a (meth) acryl group.
As a fourth aspect, the present invention relates to the thermosetting resin material according to the third aspect, in which the monomer A is a divinyl compound or a di (meth) acrylate compound.
As a 5th viewpoint, it is related with the thermosetting resin material as described in a 2nd viewpoint which uses the said monomer C in the ratio of 5-300 mol% with respect to the number-of-moles of the said monomer A. FIG.
As a sixth aspect, the present invention relates to the thermosetting resin material according to the fifth aspect, in which the monomer C is a compound having at least one of either a vinyl group or a (meth) acryl group.
As a seventh aspect, the present invention relates to the thermosetting resin material according to the sixth aspect, in which the monomer C is a compound represented by the following formula [1].

(In the formula [1], R ¹ represents a hydrogen atom or a methyl group, and R ² is substituted with a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a carboxyl group, or a hydroxy group. Represents an optionally substituted alkyl group having 1 to 20 carbon atoms.)
As an eighth aspect, the present invention relates to the thermosetting resin material according to any one of the first aspect to the seventh aspect, in which the polymerization initiator B is an azo polymerization initiator.
As a ninth aspect, the polymerization initiator B is 4,4′-azobis (4-cyanovaleric acid).
It is related with the thermosetting resin material as described in an 8th viewpoint.
As a tenth aspect, a monomer A having two or more radically polymerizable double bonds in the molecule, and a polymerization initiator B having a carboxyl group in the molecule of 5 to 200 mol% based on the number of moles of the monomer A It is related with the reaction agent (a1) containing the hyperbranched polymer which has a carboxyl group at the molecular terminal obtained by superposing | polymerizing in presence of this.
As an eleventh aspect, a monomer A having two or more radical polymerizable double bonds in the molecule, and a monomer C having a carboxyl group or a hydroxy group and at least one radical polymerizable double bond in the molecule, Reaction comprising a highly branched polymer having a carboxyl group at the molecular end, obtained by polymerizing in the presence of a polymerization initiator B having a carboxyl group in the molecule of 5 to 200 mol% relative to the number of moles of the monomer A It relates to the agent (a2).
As a twelfth aspect, a thermosetting resin composition obtained by mixing the reactive agent (a1) or the reactive agent (a2) according to any one of the first to ninth aspects and the reactive agent (b). Related to things.
As a thirteenth aspect, the molar equivalent of the carboxyl group of the hyperbranched polymer contained in the reactant (a1) or (a2) with respect to the number of moles of the isocyanate group of the polyfunctional isocyanate compound contained in the reactant (b). Is related to the thermosetting resin composition according to the twelfth aspect.
As a 14th viewpoint, it is related with the cured film obtained by thermosetting the thermosetting resin composition as described in a 12th viewpoint or a 13th viewpoint.
As a fifteenth aspect, a monomer A having two or more radically polymerizable double bonds in the molecule, and a polymerization initiator B having a carboxyl group in the molecule of 5 to 200 mol% with respect to the number of moles of the monomer A The present invention relates to a method for producing a cured resin, which comprises curing a hyperbranched polymer having a carboxyl group at the molecular end obtained by polymerizing in the presence of a polyfunctional isocyanate compound at an elevated temperature and curing.
As a sixteenth aspect, a monomer A having two or more radical polymerizable double bonds in the molecule, and a monomer C having a carboxyl group or a hydroxy group and at least one radical polymerizable double bond in the molecule, A highly branched polymer having a carboxyl group at the molecular end, obtained by polymerizing in the presence of a polymerization initiator B having a carboxyl group in the molecule of 5 to 200 mol% relative to the number of moles of the monomer A, is increased. The present invention relates to a method for producing a cured resin, which comprises reacting with a polyfunctional isocyanate compound at a given temperature and curing.
As a seventeenth aspect, a monomer A having two or more radically polymerizable double bonds in the molecule (excluding divinylbenzene) and 5-200 mol% of carboxyl in the molecule with respect to the number of moles of the monomer A The present invention relates to a hyperbranched polymer having a carboxyl group at the molecular end obtained by polymerization in the presence of a polymerization initiator B having a group.
As an eighteenth aspect, a monomer A having two or more radical polymerizable double bonds in the molecule, and a monomer C having a carboxyl group or a hydroxy group and at least one radical polymerizable double bond in the molecule, The present invention relates to a hyperbranched polymer having a carboxyl group at the molecular end obtained by polymerization in the presence of a polymerization initiator B having a carboxyl group in the molecule of 5 to 200 mol% relative to the number of moles of the monomer A.

The thermosetting resin material of the present invention does not require a catalyst necessary for the reaction (curing) of a conventional polyurethane material, that is, a polyol compound and an isocyanate compound, and at a relatively low temperature compared to the curing temperature of the polyurethane material. Also, the curing is accelerated promptly and a three-dimensional crosslinked structure can be formed.
In addition, the hyperbranched polymer having a carboxyl group at the terminal contained in the reactant (a1) or (a2) of the present invention is more aggressive than the conventional linear polymer generally in a string shape. Since a branched structure is introduced into the structure, there is less entanglement between molecules compared to a linear polymer, and it is stable. For this reason, the reactive agent (a1) or (a2) of the present invention has high solubility and dispersibility in an organic solvent, and is a reactive agent containing a polyfunctional isocyanate compound used for a thermosetting resin material ( It is excellent in mixing and dispersibility with b).
In the thermosetting resin composition of the present invention, the carboxyl group of the hyperbranched polymer contained in the reactant (a1) or (a2) and the isocyanate group of the polyfunctional isocyanate compound contained in the reactant (b) are further added. The chemical reaction (curing) can proceed easily and at a relatively low reaction temperature without requiring any special catalyst. Moreover, the cured film of the present invention obtained by thermosetting the composition can be very excellent in transparency.

  Further, the hyperbranched polymer can be used to form a thin film structure as it is by a coating / drying operation, taking advantage of the characteristics of a polymer compound. Moreover, the hyperbranched polymer of the present invention is soluble not only in N, N-dimethylformamide (DMF) and tetrahydrofuran (THF), but also in acetone and methanol. And a thin film can be formed.

FIG. 1 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 1 produced in Synthesis Example 1. 2 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 2 produced in Example 1. FIG. FIG. 3 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 3 produced in Example 2. FIG. 4 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 4 produced in Example 3. FIG. 5 is a diagram showing a ¹³ C NMR spectrum of the linear polymer 1 produced in Comparative Synthesis Example 1.

<Thermosetting resin material>
The thermosetting resin material of the present invention comprises a monomer A having two or more radically polymerizable double bonds in the molecule, and a carboxyl group in the molecule of 5 to 200 mol% relative to the number of moles of the monomer A. It comprises a combination of a reactive agent (a1) containing a highly branched polymer having a carboxyl group at the molecular end and a reactive agent (b) containing a polyfunctional isocyanate compound, obtained by polymerizing in the presence of the polymerization initiator B having Is.
Alternatively, the thermosetting resin material of the present invention comprises a monomer A having two or more radical polymerizable double bonds in the molecule, a carboxyl group or a hydroxy group and at least one radical polymerizable double bond in the molecule. And a monomer C having a carboxyl group at the molecular terminal obtained by polymerizing the monomer C in the presence of a polymerization initiator B having a carboxyl group in the molecule of 5 to 200 mol% relative to the number of moles of the monomer A. Reactant containing hyperbranched polymer having (a
2) and a combination of a reactive agent (b) containing a polyfunctional isocyanate compound.

[Reactant (a1) and Reactant (a2)]
The reactive agent (a1) or the reactive agent (a2) used in the thermosetting resin material is carboxylated at the molecular end obtained by polymerizing monomer A or monomer A and monomer C in the presence of polymerization initiator B. It includes a hyperbranched polymer having groups. The hyperbranched polymer is a so-called initiator fragment-embedded hyperbranched polymer, and has a fragment of the polymerization initiator B used for polymerization at the terminal.

(Monomer A)
In the present invention, the monomer A having two or more radically polymerizable double bonds in the molecule preferably has one or both of a vinyl group and a (meth) acryl group, and in particular, a divinyl compound or di (meta). ) An acrylate compound is preferred. In the present invention, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.

Examples of such a monomer A include organic compounds shown in the following (A1) to (A7).
(A1) Vinyl hydrocarbon:
(A1-1) Aliphatic vinyl hydrocarbon; isoprene, butadiene, 3-methyl-1,2-butadiene, 2,3-dimethyl-1,3-butadiene, 1,2-polybutadiene, pentadiene, hexadiene, octadiene, etc. .
(A1-2) Alicyclic vinyl hydrocarbon; cyclopentadiene, cyclohexadiene, cyclooctadiene, norbornadiene and the like.
(A1-3) Aromatic vinyl hydrocarbons: divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, divinylbiphenyl, divinylnaphthalene, divinylfluorene, divinylcarbazole, divinylpyridine and the like.
(A2) Vinyl ester, allyl ester, vinyl ether, allyl ether, vinyl ketone:
(A2-1) Vinyl ester; divinyl adipate, divinyl maleate, divinyl phthalate, divinyl isophthalate, divinyl itaconate, vinyl (meth) acrylate and the like.
(A2-2) Allyl ester; diallyl maleate, diallyl phthalate, diallyl isophthalate, diallyl adipate, allyl (meth) acrylate, and the like.
(A2-3) Vinyl ether; divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether and the like.
(A2-4) Allyl ether; diallyl ether, diallyloxyethane, triallyloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetramethallyloxyethane and the like.
(A2-5) Vinyl ketone; divinyl ketone, diallyl ketone and the like.
(A3) (Meth) acrylic acid ester:
Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) Acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, alkoxytitanium tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) ) Acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, Glycol di (meth) acrylate, 2-hydroxy -
1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di (meth) acryloyloxypropane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, un Decylenoxyethylene glycol di (meth) acrylate, bis [4- (meth) acryloylthiophenyl] sulfide, bis [2- (meth) acryloylthioethyl] sulfide, 1,3-adamantanediol di (meth) acrylate, 1 , 3-adamantane dimethanol di (meth) acrylate and the like. (A4) Vinyl compound having a polyalkylene glycol chain:
Polyethylene glycol (molecular weight 300) di (meth) acrylate, polypropylene glycol (molecular weight 500) di (meth) acrylate, and the like.
(A5) Nitrogen-containing vinyl compound:
Diallylamine, diallyl isocyanurate, diallyl cyanurate, methylenebis (meth) acrylamide, bismaleimide and the like.
(A6) Silicon-containing vinyl compound:
Dimethyldivinylsilane, divinylmethylphenylsilane, diphenyldivinylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,1,3,3-tetraphenyldisilazane , Dietodivinylsilane and the like.
(A7) Fluorine-containing vinyl compound:
1,4-divinylperfluorobutane, 1,6-divinylperfluorohexane, 1,8-divinylperfluorooctane, and the like.

Among these, preferred are the aromatic vinyl hydrocarbon compounds of the above group (A1-3), vinyl esters, allyl esters, vinyl ethers, allyl ethers and vinyl ketones of the group (A2), (meth) acrylic of the group (A3). An acid ester, a vinyl compound having a polyalkylene glycol chain of (A4) group, and a nitrogen-containing vinyl compound of (A5) group.
Particularly preferred are divinylbenzene belonging to group (A1-3), diallyl phthalate belonging to group (A2), ethylene glycol di (meth) acrylate belonging to group (A3), and tricyclodecane dimethanol di (meth) acrylate. 2-hydroxy-1,3-di (meth) acryloyloxypropane. Among these, divinylbenzene, ethylene glycol di (meth) acrylate and 2-hydroxy-1,3-di (meth) acryloyloxypropane are preferable.

(Monomer C)
In the present invention, the monomer C having a carboxyl group or a hydroxy group and at least one radical polymerizable double bond in the molecule preferably has at least one of either a vinyl group or a (meth) acryl group. Is preferred.

As such a monomer C, the organic compound shown to the following (C1) thru | or (C3) is illustrated, for example.
(C1) (Meth) acrylic acids:
(Meth) acrylic acid, itaconic acid, 2-trifluoromethyl acrylic acid, 2-ethyl acrylic acid, 2-propyl acrylic acid, 2-bromomethyl acrylic acid, 2-acetamidoacrylic acid, 2-ethylacryloyl chloride, 3, 3-dimethyl (meth) acryloyl chloride and the like.
(C2) Hydroxy group-containing (meth) acrylic acid esters:
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- (4-benzoyl-3-hydroxyphenoxy) ethyl ( (Meth) acrylate, 2-hydroxypropyl = 2- (meth) acryloyloxyethyl phthalate, caprolactone 2- (meth) acryloyloxyethyl ester hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-acryloyloxy-2-hydroxypropyl (meth) acrylate, methyl = 3-hydroxy-2-methylenebutyrate, diethyleneglycol Rumono (meth) acrylate, triethylene glycol mono (meth) acrylate, 1,3-butanediol mono (meth) acrylate, tetramethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, neopentyl glycol mono (meta) ) Acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and the like.
(C3) Hydroxy group-containing vinyl compound:
Hydroxystyrene, allyl alcohol, methallyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, 2-hydroxyethylpropenyl Ether etc.
(C4) Vinylbenzoic acids:
3-vinyl benzoic acid, 4-vinyl benzoic acid and the like.

The monomer C is particularly preferably a compound represented by the formula [1].
Accordingly, among these compounds exemplified above, preferred are the compounds described in the above (C1) group and (C2) group, and particularly preferred are (meth) acrylic acid, 2-hydroxyethyl ( And (meth) acrylate.

In the present invention, instead of the monomer C having a carboxyl group or hydroxy group and at least one radical polymerizable double bond in the molecule, a group in which the carboxyl group or hydroxy group is protected with a protective group, A monomer having a carboxyl group or hydroxy group protected by a protecting group in the molecule and at least one radical polymerizable double bond (referred to as monomer D) can be used.
In that case, after polymerization with the monomer A, the protective group in the carboxyl group or hydroxy group protected by the protective group is removed to form a carboxyl group or hydroxy group.
The protective group for the carboxyl group is not particularly limited, and examples thereof include ester groups such as a benzyl ester group, a cumyl ester group, an enol ester group, an acetal ester group, and a tertiary alkyl ester group. Tertiary alkyl ester group.
Further, the protective group for the hydroxy group is not particularly limited, but examples thereof include ether groups such as benzyl ether group, tertiary alkyl ether group and alkoxyalkyl ether group, acetal groups such as 2-tetrahydropyranyloxy group, acetoxy Group, an acyloxy group such as a pivaloyloxy group and a benzoyloxy group, and preferably an acyloxy group.
Examples of such a monomer D include tert-butyl (meth) acrylate, 2-tert-butoxycarbonylethyl (meth) acrylate, 2-tert-butoxyethyl (meth) acrylate, and 2-methoxymethoxyethyl (meth) acrylate. , 2-pivaloyloxyethyl (meth) acrylate and the like.

  In the present invention, the ratio of copolymerizing the monomer A and the monomer C is preferably 5 to 300 mol% of the monomer C with respect to the number of moles of the monomer A from the viewpoint of polymerizability and curability. Preferably, it is used at a ratio of 10 to 150 mol%.

(Polymerization initiator B)
As the polymerization initiator B having a carboxyl group in the molecule in the present invention, an azo polymerization initiator having a carboxyl group is preferably used, and in particular, 4,4′-azobis (4-cyanovaleric acid), 2,2 ′. -Azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate is preferred.

In the present invention, in addition to the azo polymerization initiator B having a carboxyl group in the molecule,
For example, other azo polymerization initiators (not having a carboxyl group) listed in the following (1) to (6) may be used.
(1) Azonitrile compound:
2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis ( 1-cyclohexanecarbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile and the like.
(2) Azoamide compound:
2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- [2- ( 1
-Hydroxybutyl)] propionamide}, 2,2′-azobis [2-methyl-N- (
2-hydroxyethyl) propionamide], 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), 2 , 2'-azobis (N-cyclohexyl-2-methylpropionamide) and the like.
(3) Cyclic azoamidine compound:
2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2′-azobis [2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) Propane], 2,2′-azobis (1-imino-1-pyrrolidino-2-
Methylpropane) dihydrochloride and the like.
(4) Azoamidine compound:
2,2′-azobis (2-methylpropionamidine) dihydrochloride and the like.
(5) Other:
Dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis (2,4,4-trimethylpentane), 1,1′-azobis (1-acetoxy-1-phenylethane), dimethyl 1,1′-azobis (1-cyclohexanecarboxylate) and the like.
(6) Fluoroalkyl group-containing azo polymerization initiator:
4,4′-azobis (2-cyanopentanoic acid 2- (perfluoromethyl) ethyl), 4,
4′-azobis (2-cyanopentanoic acid 2- (perfluorobutyl) ethyl), 4,4′-azobis (4-cyanopentanoic acid 2- (perfluorohexyl) ethyl) and the like.

The polymerization initiator B is used in an amount of 5 to 200 mol% with respect to the number of moles of the monomer A, preferably 15 to 200 mol%, more preferably 15 to 170 mol%, still more preferably 50 to Used in an amount of 100 mol%.
In addition, in addition to the polymerization initiator B having a carboxyl group in the molecule, when using other polymerization initiators (having no carboxyl group), the carboxyl group is added in the molecule with respect to the total number of moles of the polymerization initiator to be used. It is preferable to use the polymerization initiator B having a mole number of 50% or more.

(Method for producing hyperbranched polymer having carboxyl group at molecular end)
The hyperbranched polymer having a carboxyl group at the molecular end of the present invention is obtained by polymerizing in the presence of a predetermined amount of the polymerization initiator B with respect to the monomer A or the monomer A and the monomer C. Known methods such as solution polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization and the like can be mentioned, among which solution polymerization or precipitation polymerization is preferable. In particular, it is preferable to carry out the reaction by solution polymerization in an organic solvent from the viewpoint of molecular weight control.
Examples of organic solvents used here include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit, and cyclohexane Solvent: Halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, orthodichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate , Ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and other ester or ester ether solvents; diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cello Ether solvents such as rub, butyl cellosolve, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone; methanol, ethanol, n-propanol, isopropanol, alcohol solvents such as n-butanol, isobutanol, tert-butanol, 2-ethylhexyl alcohol, benzyl alcohol; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide And heterocyclic compound solvents such as N-methyl-2-pyrrolidone, and a mixed solvent of two or more thereof.
Of these, preferred are aromatic hydrocarbon solvents, halogen solvents, ester solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, etc., and particularly preferred are toluene. , Xylene, orthodichlorobenzene, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, 1,4-dioxane, methyl cellosolve, methyl isobutyl ketone, N, N-dimethylformamide, N, N- Dimethylacetamide and the like.

When the polymerization reaction is performed in the presence of an organic solvent, the content of the organic solvent in the entire polymerization reaction product is preferably 1 to 500 parts by weight, more preferably 5 to 300 parts by weight, with respect to 1 part by weight of the monomer A. It is.
The polymerization reaction is carried out under normal pressure, under pressure and under pressure, or under reduced pressure, and is preferably carried out under normal pressure in view of simplicity of the apparatus and operation. Further, preferably carried out in an atmosphere of inert gas such as N _2.
The temperature of the polymerization reaction is preferably 50 to 200 ° C, more preferably 70 to 150 ° C.
More preferably, the temperature of the polymerization reaction is 20 ° C. or more higher than the 10-hour half-life temperature of the polymerization initiator B, and more specifically, the monomer A, the monomer C, and the polymerization initiator B. It is preferable to perform the polymerization reaction by dropping a solution containing the organic solvent into the organic solvent maintained at a temperature 20 ° C. or more higher than the 10-hour half-life temperature of the polymerization initiator B.
It is even more preferable to carry out the polymerization reaction at the reflux temperature of the organic solvent under a reaction pressure.
After completion of the polymerization reaction, the obtained hyperbranched polymer having a carboxyl group at the molecular end is collected by an arbitrary method, and post-treatment such as washing is performed as necessary. Examples of a method for recovering the polymer from the reaction solution include a method such as reprecipitation.

  The weight average molecular weight (hereinafter abbreviated as Mw) of the obtained hyperbranched polymer having a carboxyl group at the molecular end is preferably 1,000 to 200,000, more preferably 2 in terms of polystyrene by gel permeation chromatography (GPC). 1,000 to 100,000, most preferably 3,000 to 60,000.

The reactants (a1) and (a2) containing the hyperbranched polymer thus obtained are also objects of the present invention. That is, in the presence of a monomer A having two or more radically polymerizable double bonds in the molecule and a polymerization initiator B having a carboxyl group in the molecule of 5 to 200 mol% relative to the number of moles of the monomer A. And (a1) containing a hyperbranched polymer having a carboxyl group at the molecular end, monomer A having two or more radically polymerizable double bonds in the molecule, and A monomer C having a carboxyl group or a hydroxy group and at least one radical-polymerizable double bond, and a polymerization initiator B having a carboxyl group in the molecule of 5 to 200 mol% relative to the number of moles of the monomer A The reaction agent (a2) containing a hyperbranched polymer having a carboxyl group at the molecular end obtained by polymerizing in the presence is also an object of the present invention.

  Furthermore, the present invention is also directed to each hyperbranched polymer obtained by the above-described method. That is, in the presence of a monomer A having two or more radically polymerizable double bonds in the molecule and a polymerization initiator B having a carboxyl group in the molecule of 5 to 200 mol% relative to the number of moles of the monomer A. A highly branched polymer having a carboxyl group at the molecular end obtained by polymerizing (except for divinylbenzene as monomer A), and monomer A having two or more radically polymerizable double bonds in the molecule, and Polymerization of a monomer having a carboxyl group or hydroxy group and at least one radical polymerizable double bond in the molecule, and having a carboxyl group in the molecule of 5 to 200 mol% relative to the number of moles of the monomer A A hyperbranched polymer having a carboxyl group at the molecular end obtained by polymerizing in the presence of initiator B is also a polymer of the present invention. It is an elephant.

In the present invention, the reactants (a1) and (a2) can contain an organic solvent capable of dissolving or dispersing the polymer in addition to the above-described hyperbranched polymer.
The organic solvent that can be used at this time can be appropriately selected from the organic solvents used in the above-mentioned (manufacturing method of the hyperbranched polymer having a carboxyl group at the molecular terminal), but is combined with the later-described reactant (b) Considering aromatic hydrocarbon solvents, aliphatic or alicyclic hydrocarbon solvents, halogen solvents, ester or ester ether solvents, ether solvents, ketone solvents, amide solvents, sulfoxide solvents It is desirable to be selected. Examples of preferred solvents include ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, butyl cellosolve, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone , N, N-dimethylformamide, dimethyl sulfoxide and the like.
These solvents may be used alone, or two or more kinds of solvents may be mixed.
In the reactants (a1) and (a2), the amount of the organic solvent in which the hyperbranched polymer is dissolved or dispersed is the amount of the reactant (b) used later and the amount contained in the reactant (b). It is optional depending on the concentration of the functional isocyanate compound. Usually, the concentration of the hyperbranched polymer is 0.001 to 90% by mass with respect to the total mass (total mass) of the hyperbranched polymer and the solvent, preferably Is 0.002-80 mass%, More preferably, it is 0.005-70 mass%.

[Reactant (b)]
The reactive agent (b) used for the thermosetting resin material includes a polyfunctional isocyanate compound.
Here, the polyfunctional isocyanate compound is not particularly limited as long as it is an aromatic, aliphatic, or alicyclic compound having two or more isocyanate groups in one molecule. For example, in the production of polyurethane resin The various isocyanate compounds which can be used as a main ingredient can be mentioned.
Examples of such polyfunctional isocyanate compounds include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate. Lysine diisocyanate (2,6-diisocyanatomethylcaproate), bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl = 2,6-diisocyanatohexa Noate, isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane-4,4'-diisocyanate (Hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) = 4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate, Examples include, but are not limited to, m- and / or p-xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate.
In addition, modified isocyanate compounds such as urethane-modified products, allophanate-modified products, carbodiimide-modified products, burette-modified products, and isocyanurate-modified products of these polyfunctional isocyanate compounds can also be used.
The said polyisocyanate compound and its modified body can be used individually or in combination of 2 or more types.

In addition to the polyfunctional isocyanate compound, the reactant (b) can contain an organic solvent capable of dissolving or dispersing the compound.
Examples of the organic solvent that can be used at this time include the same ones as described in the above-mentioned reactants (a1) and (a2), and preferable examples of the solvent include the aforementioned reactants (a1) and (a1). The thing similar to what was described in (a2) can be mentioned. These solvents may be used alone, or two or more kinds of solvents may be mixed.
In the above-mentioned reactant (b), the amount of the organic solvent for dissolving or dispersing the polyfunctional isocyanate compound is the amount of the above-mentioned reactant (a1) or (a2) used, the reactant (a1) or (a2). The concentration of the hyperbranched polymer is 0.001 to 90% by mass with respect to the total mass (total mass) of the hyperbranched polymer and the solvent. Preferably, it is 0.002-80 mass%, More preferably, it is 0.005-70 mass%.

<Thermosetting resin composition and cured film>
The present invention also relates to a thermosetting resin composition obtained by mixing the reactive agent (a1) or the reactive agent (a2) and the reactive agent (b).
In the thermosetting resin composition of the present invention, the hyperbranched polymer contained in the reactant (a1) or (a2) with respect to the number of moles of isocyanate groups of the polyfunctional isocyanate compound contained in the reactant (b). The molar equivalent of the carboxyl group is preferably from 0.01 to 10, more preferably from 0.05 to 5, and further preferably from 0.1 to 2.

  In addition, the thermosetting resin composition of the present invention may contain one or more pigments and dyes as necessary, as long as the effects of the present invention are not impaired, or other components as necessary. Add one or more organic solvents, various additives such as UV absorbers, light stabilizers, antioxidants, surfactants, surface modifiers, curing reaction catalysts, antistatic agents, perfumes, rheology modifiers, etc. Can be used. These additive components are preferably contained in the reactant (a1) or (a2).

Thus, the prepared thermosetting resin composition is preferably used for subsequent formation of a cured film after filtration using a filter having a pore size of about 0.2 μm.

The present invention also relates to a cured film obtained by thermosetting the thermosetting resin composition.
As a specific method for forming the cured film of the present invention, after first preparing the thermosetting resin composition, cast coating method, spin coating method, blade coating method, dip coating method on the composition, A coating film is obtained by coating by a roll coating method, a bar coating method, a die coating method, an ink jet method, a printing method (such as relief printing, intaglio printing, planographic printing, and screen printing). Among these coating methods, the spin coating method is preferable. In the case of using the spin coating method, since it can be applied in a single time, even a highly volatile solution can be used, and there is an advantage that highly uniform application can be performed.
Examples of the substrate include plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, slate, etc. Can be mentioned. The shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded body.

After forming the coating film, the coating film is subsequently heat-treated to obtain a cured film. As conditions for this heat treatment, for example, a heating temperature and a heating time appropriately selected from the range of a temperature of 70 to 160 ° C. and a time of 0.3 to 60 minutes are adopted. The heating temperature and the heating time are preferably 80 to 150 ° C., 0.5 to 30 minutes, or 1 to 10 minutes. The thickness of the formed cured film is not particularly limited, but may be 0.1 to 30 μm, for example. Yes, for example, 0.2 to 10 μm, and further, for example, 0.2 to 5 μm.

<Method for producing cured resin>
The present invention further includes a monomer A having two or more radically polymerizable double bonds in the molecule, and a polymerization initiator having a carboxyl group in the molecule of 5 to 200 mol% based on the number of moles of the monomer A. A method for producing a cured resin, which comprises curing a hyperbranched polymer having a carboxyl group at the molecular end obtained by polymerizing in the presence of B by reacting with a polyfunctional isocyanate compound at an elevated temperature. Related.
The present invention also includes a monomer A having two or more radical polymerizable double bonds in the molecule, and a monomer C having a carboxyl group or a hydroxy group and at least one radical polymerizable double bond in the molecule. A highly branched polymer having a carboxyl group at the molecular end, obtained by polymerizing in the presence of a polymerization initiator B having a carboxyl group in the molecule of 5 to 200 mol% relative to the number of moles of the monomer A, is increased. The present invention also relates to a method for producing a cured resin, which comprises curing by reacting with a polyfunctional isocyanate compound at a determined temperature.
Here, the hyperbranched polymer having a carboxyl group at the molecular end corresponds to the hyperbranched polymer described in [Reactant (a1) and Reactant (a2)].

In the method for producing a cured resin of the present invention, a catalyst required for reacting a highly branched polymer with a polyfunctional isocyanate compound and reacting with a general polyol compound and polyisocyanate is not required. That is, a cured resin is produced using only the highly branched polymer having a carboxyl group at the terminal and a polyfunctional isocyanate compound.
In the present invention, in the production of the cured resin, a highly branched polymer having a carboxyl group at the molecular end and a polyfunctional isocyanate compound are heated by heating at a temperature of 70 ° C. to 160 ° C. for a time of 0.3 to 60 minutes. React to produce a cured resin.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.

(1) Gel permeation chromatography (GPC)
Device: HLC-8220GPC manufactured by Tosoh Corporation
Column: Shodex KF-804L, KF-805L
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Detector: RI
(2) ¹³ C NMR spectrum apparatus: JNM-ECA700 manufactured by JEOL Datum Co., Ltd.
Solvent: DMSO-d ₆ (Synthesis Example 1, Examples 1 to 3), CDCl ₃ (Comparative Synthesis Example 1)
Internal standards: DMSO-d ₆ (39.7 ppm), CDCl ₃ (77.0 ppm)
(3) Spin coater device: MS-A100 manufactured by Mikasa Co., Ltd.
(4) Hot plate apparatus: MH-180CS, MH-3CS manufactured by AS ONE Corporation
(5) Film thickness measurement device: Fine shape measuring machine ET4000A manufactured by Kosaka Laboratory Ltd.
(6) Contact angle measurement device: VCA Optima manufactured by AST Products
Measurement temperature: 20 ° C

Abbreviations represent the following meanings.
DVB: divinylbenzene [DVB-960 manufactured by Nippon Steel Chemical Co., Ltd.]
EGDMA: Ethylene glycol dimethacrylate [1G made by Shin-Nakamura Chemical Co., Ltd.]
PGHM: 2-hydroxy-1,3-dimethacryloyloxypropane [manufactured by Shin-Nakamura Chemical Co., Ltd. 701]
HEMA: Hydroxyethyl methacrylate [manufactured by Pure Chemical Co., Ltd.]
VN: Vinyl naphthalene [manufactured by Nippon Steel Chemical Co., Ltd.]
MA: Methacrylic acid [manufactured by Kanto Chemical Co., Inc.]
ACVA: 4,4′-azobis (4-cyanovaleric acid) [V-501, manufactured by Wako Pure Chemical Industries, Ltd.]
MAIB: Dimethyl 2,2′-azobisisobutyrate [MAIB manufactured by Otsuka Chemical Co., Ltd.] F510: Branched trifunctional polyol [Kuraray Polyol F-510 manufactured by Kuraray Co., Ltd.]
P1010: linear bifunctional polyol [Kuraray Co., Ltd. Kuraray Polyol P-1010] H40: dendritic 64-functional polyol [Pertorp Boltorn (registered trademark) H40]
EGME: ethylene glycol monomethyl ether PGME: propylene glycol monomethyl ether MEK: ethyl methyl ketone THF: tetrahydrofuran DMAc: N, N-dimethylacetamide DMF: N, N-dimethylformamide

[Synthesis Example 1] Synthesis of hyperbranched polymer 1 using DVB and ACVA A 1 L reaction flask was charged with 391 g of EGME, and nitrogen was allowed to flow for 5 minutes with stirring, followed by heating until the internal liquid was refluxed (approximately 120 ° C).
In another 500 mL reaction flask, 3.9 g (30 mmol) of DVB as monomer A, 6.7 g (24 mmol) of ACVA as initiator B, and 391 g of EGME were charged, and nitrogen substitution was performed by flowing nitrogen for 5 minutes while stirring.
The contents were added dropwise from the 500 mL reaction flask charged with DVB and ACVA into the EGME refluxed in the 1 L reaction flask using a dropping pump over 60 minutes. After completion of dropping, the mixture was aged for 1 hour.
Next, after 742 g of EGME was distilled off from this reaction solution using a rotary evaporator, it was added to 430 g of a water / acetone mixture (volume ratio 9: 1) to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum-dried to obtain 9.6 g of the desired product (highly branched polymer 1) as a white powder.
A ¹³ C NMR spectrum of the obtained target product is shown in FIG. The unit structure composition (molar ratio) of the hyperbranched polymer 1 represented by the following structural formula calculated from the ¹³ C NMR spectrum was DVB unit: ACVA unit = 50: 50. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the target product was 8,100, and the degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) was 2.0.

式中、黒点は結合端を表す。

In the formula, a black dot represents a coupling end.

[Example 1] Synthesis of hyperbranched polymer 2 using EGDMA and ACVA A 300 mL reaction flask was charged with 89 g of EGME, and nitrogen was allowed to flow for 5 minutes with stirring until the internal solution was refluxed (approximately 120 ° C).
In another 200 mL reaction flask, 6.0 g (30 mmol) of EGDMA as monomer A, 4.2 g (15 mmol) of ACVA as initiator B, and 89 g of EGME were charged, and nitrogen substitution was performed by flowing nitrogen for 5 minutes while stirring.
From the 200 mL reaction flask charged with EGDMA and ACVA, the contents were dropped into the EGME refluxed in the 300 mL reaction flask using a dropping pump over 60 minutes. After completion of dropping, the mixture was aged for 1 hour.
Next, 140 g of EGME was distilled off from this reaction solution using a rotary evaporator, and then added to 300 g of a water / acetone mixture (volume ratio 9: 1) to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum dried to obtain 5.5 g of the desired product (highly branched polymer 2) as a white powder.
The ¹³ C NMR spectrum of the obtained target product is shown in FIG. The unit structure composition (molar ratio) of the hyperbranched polymer 2 represented by the following structural formula calculated from the ¹³ C NMR spectrum was EGDMA unit: ACVA unit = 61: 29. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the target object was 5,300, and dispersion degree: Mw / Mn was 2.4.

式中、黒点は結合端を表す。

In the formula, a black dot represents a coupling end.

[Example 2] Synthesis of hyperbranched polymer 3 using PGHM and ACVA A 300 mL reaction flask was charged with 68 g of EGME, and nitrogen was poured for 5 minutes with stirring, followed by heating until the internal liquid was refluxed (approximately 120 ° C).
In a separate 100 mL reaction flask, 6.9 g (30 mmol) of PGHM as monomer A was added.
), 3.4 g (12 mmol) of ACVA as initiator B and 68 g of EGME were charged, and nitrogen substitution was performed by flowing nitrogen for 5 minutes while stirring.
The contents were dropped into the EGME refluxed in the 300 mL reaction flask from the 100 mL reaction flask charged with PGHM and ACVA over 60 minutes using a dropping pump. After completion of dropping, the mixture was aged for 1 hour.
Next, 120 g of EGME was distilled off from this reaction solution using a rotary evaporator, and then added to 340 g of a water / acetone mixture (volume ratio 9: 1) to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum dried to obtain 6.5 g of the desired product (highly branched polymer 3) as a white powder.
The ¹³ C NMR spectrum of the obtained target product is shown in FIG. The unit structure composition (molar ratio) of the hyperbranched polymer 3 represented by the following structural formula calculated from the ¹³ C NMR spectrum was PGHM unit: ACVA unit = 61: 29. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 3,600, and dispersion degree: Mw / Mn was 2.0.

式中、黒点は結合端を表す。

In the formula, a black dot represents a coupling end.

[Example 3] Synthesis of hyperbranched polymer 4 using PGHM, HEMA and ACVA In Example 2, except that HEMA 2.0 g (15 mmol) was added as monomer C, the same operation as in Example 2 was carried out to obtain a white powder. 5.0 g of the desired product (hyperbranched polymer 4) was obtained.
The ¹³ C NMR spectrum of the obtained target product is shown in FIG. The unit structure composition (molar ratio) of the hyperbranched polymer 4 represented by the following structural formula calculated from the ¹³ C NMR spectrum was PGHM unit: HEMA unit: ACVA unit = 50: 30: 20. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the target object was 4,100, and dispersion degree: Mw / Mn was 2.0.

式中、黒点は結合端を表す。

In the formula, a black dot represents a coupling end.

[Comparative Synthesis Example 1] Synthesis of linear polymer 1 having a carboxyl group Into a 300 mL reaction flask, VN 61.7 g (400 mmol), MA 8.6 g (1
00 mmol) and 164 g of DMAc, and stirred to obtain a homogeneous solution. To this solution, 1.8 g (8 mmol) of MAIB was added, and the atmosphere in the flask was replaced with nitrogen. Then, it stirred at 70 degreeC for 11 hours, and stood to cool to room temperature (about 25 degreeC).
Next, this reaction liquid was added to 1,500 g of methanol to precipitate the polymer in a slurry state. The slurry was filtered under reduced pressure. This filtrate was dissolved in 225 g of THF and added again to 1,500 g of methanol to precipitate the polymer in a slurry state. The slurry was filtered under reduced pressure and dried in vacuo to obtain 32.0 g of the desired product (linear polymer 1) as a yellow powder.
The ¹³ C NMR spectrum of the obtained target product is shown in FIG. The unit structure composition (molar ratio) of the linear polymer 1 represented by the following structural formula calculated from the ¹³ C NMR spectrum was VN unit: MA unit = 80: 20. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the target object was 14,700, and dispersion degree: Mw / Mn was 2.0.

式中、黒点は結合端を表す。

In the formula, a black dot represents a coupling end.

[Example 4] Solvent solubility of hyperbranched polymers 1 to 4 For the hyperbranched polymers 1 to 4 obtained in Synthesis Example 1 and Examples 1 to 3, the solubility in each solvent shown in Table 1 was evaluated. In the test, each hyperbranched polymer was mixed with each solvent so as to have a concentration of 10% by mass, stirred at 25 ° C. for 1 minute, and then visually evaluated according to the following criteria. The results are also shown in Table 1.
[Evaluation criteria]
○: A transparent solution is formed and dissolved well. ×: Undissolved residue

Comparative Example 1 Solvent Solubility of Linear Polymer 1 The linear polymer 1 obtained in Comparative Synthesis Example 1 was evaluated in the same manner as in Example 4. The results are also shown in Table 1.

[Example 5] Production of single thin film using hyperbranched polymers 1 to 4 For the hyperbranched polymers 1 to 4 obtained in Synthesis Example 1 and Examples 1 to 3, 5 mass% PGME solutions (varnishes) were respectively prepared. did. This varnish was filtered and spin-coated on a silicon wafer (slope for 5 seconds, then 1,500 rpm × 30 seconds, and further slope for 5 seconds) to obtain a coating film. The solvent was removed by heat-treating this coating film at 100 ° C. for 30 minutes to form a film. For any hyperbranched polymer, a uniform film without surface roughness was obtained. Table 2 shows the thickness of each thin film obtained.

[Examples 6 to 8] Curing of hyperbranched polymer 1 with polyisocyanate The following liquid A and liquid B were prepared.
Liquid A: 10% by mass of highly branched polymer 1 synthesized according to Synthesis Example 1 MEK solution B liquid: 10% by mass of polyisocyanate [Coronate 2770 (isocyanate group content: 19.4% by mass) manufactured by Nippon Polyurethane Industry Co., Ltd.] MEK solution Next, 2.5 g of liquid A and 2.2 g of liquid B are mixed so that the molar ratio of the carboxyl group in liquid A to the isocyanate group in liquid B is 1: 1, and uniform curability is obtained. A composition was prepared.
This curable composition was spin-coated on a 2 cm × 2 cm glass substrate (slope 5 seconds, then 2,000 rpm × 30 seconds, and further slope 5 seconds) to obtain a coating film. The coated film was heated at 100 ° C. (Example 6), 125 ° C. (Example 7), and 150 ° C. (Example 8) for 5 minutes to prepare a cured film.
The obtained cured film was immersed in acetone for 30 seconds, and the degree of curing (= film thickness after immersion ÷ film thickness before immersion × 100) was evaluated from the film thickness before and after immersion. Furthermore, the light transmittance and the HAZE value of the film after immersion were measured. Moreover, about the cured film (Example 8) at 150 degreeC, the contact angle of water after acetone immersion was measured. The results are also shown in Table 3.

[Examples 9 to 11] Curing of hyperbranched polymer 2 with polyisocyanate In Examples 6 to 8, liquid A was mixed with 10% by mass MEK solution of hyperbranched polymer 2, and the amount of liquid A was mixed with liquid B. .2 g were operated and evaluated in the same manner as in Examples 6 to 8, except that each was changed. The results are also shown in Table 3.

[Examples 12 to 14] Curing of hyperbranched polymer 3 with polyisocyanate In Examples 6 to 8, A liquid was mixed with 10% by mass MEK solution of hyperbranched polymer 3 and B liquid was mixed with 7 parts. The operation and evaluation were carried out in the same manner as in Examples 6 to 8 except that the amount was changed to 0.0 g. The results are also shown in Table 3.

[Examples 15 to 17] Curing of hyperbranched polymer 4 with polyisocyanate In Examples 6 to 8, liquid A was mixed with 10% by mass MEK solution of hyperbranched polymer 4, and the amount of liquid A was mixed with liquid B. The operation and evaluation were carried out in the same manner as in Examples 6 to 8 except that the content was changed to 0.9 g. The results are also shown in Table 3.

[Comparative Examples 2 to 4] Curing of linear polymer 1 with polyisocyanate In Examples 6 to 8, A liquid is mixed with 10% by mass MEK solution of linear polymer 1 with B liquid. Was evaluated in the same manner as in Examples 6 to 8 except that 7.0g was used and the immersion solvent for the cured film was changed to THF. The results are also shown in Table 3.

[Comparative Examples 5 to 7] Curing of branched trifunctional polyol with polyisocyanate The following liquid A and liquid B were prepared.
A liquid: 10 mass% MEK solution of F510 B liquid: 10 mass% MEK solution of polyisocyanate [Nihon Polyurethane Industry Co., Ltd. coronate 2770 (isocyanate group content: 19.4 mass%)] Next, in A liquid 1.7 g of A liquid and 2.2 g of B liquid were mixed so that the molar ratio of the hydroxy group to the isocyanate group in B liquid was 1: 1 to prepare a uniform curable composition.
This curable composition was spin-coated on a 2 cm × 2 cm glass substrate (slope 5 seconds, then 2,000 rpm × 30 seconds, and further slope 5 seconds) to obtain a coating film. A cured film was produced by heating the coating film at 100 ° C. (Comparative Example 5), 125 ° C. (Comparative Example 6), and 150 ° C. (Comparative Example 7) for 5 minutes.
The obtained cured film was immersed in acetone for 30 seconds, and the degree of curing was evaluated from the film thickness before and after immersion. Furthermore, the light transmittance and the HAZE value of the film after immersion were measured. The results are also shown in Table 3.

[Comparative Examples 8 to 10] Curing of Chain Bifunctional Polyol with Polyisocyanate In Comparative Examples 5 to 7, the amount of the A liquid mixed with the B liquid in the 10 mass% MEK solution of P1010 is 5.2 g. In addition, operations and evaluations were performed in the same manner as in Comparative Examples 5 to 7 except that each was changed. The results are also shown in Table 3.

[Comparative Examples 11 to 13] Curing of dendritic 64-functional polyol with polyisocyanate The following liquid A and liquid B were prepared.
Liquid A: 10% by mass of H40 in DMF / MEK (mass ratio 7: 3) Solution B: 10% by mass of polyisocyanate [Nihon Polyurethane Industry Co., Ltd. Coronate 2770 (isocyanate group content: 19.4% by mass)] DMF / MEK (mass ratio 7: 3) solution Next, 1.1 g of A liquid and B liquid 2 so that the molar ratio of the hydroxyl group in A liquid and the isocyanate group in B liquid might become 1: 1. 2 g was mixed to prepare a uniform curable composition.
This curable composition was spin-coated on a 2 cm × 2 cm glass substrate (slope 5 seconds, then 2,000 rpm × 30 seconds, and further slope 5 seconds) to obtain a coating film. A cured film was produced by heating this coating film at 100 ° C. (Comparative Example 11), 125 ° C. (Comparative Example 12), and 150 ° C. (Comparative Example 13) for 5 minutes.
The obtained cured film was immersed in DMF for 30 seconds, and the degree of curing was evaluated from the film thickness before and after immersion. Furthermore, the light transmittance and the HAZE value of the film after immersion were measured. For the cured film at 150 ° C. (Comparative Example 13), the contact angle of water after DMF immersion was measured. The results are also shown in Table 3.

As shown in Table 3, Examples 6 to 17 cure rapidly even without a catalyst, and 75 even when the temperature is as low as 100 ° C. (Examples 6, 9, 12 and 15). A high degree of cure of at least% was shown. In each of the examples, a cured film having excellent transparency (transmittance / HAZE value) could be obtained.
On the other hand, although Comparative Examples 2 to 4 using a linear polymer having a carboxyl group at the end were cured without a catalyst, the degree of curing was only 73% even at 150 ° C.
Further, Comparative Examples 5 to 7 (branched trifunctional polyol) and Comparative Examples 8 to 10 (chain bifunctional polyol) using commercially available polyols are hardly cured even at a curing temperature of 150 ° C. Moreover, although Comparative Example 11-Comparative Example 13 (dendritic 64 functional polyol) hardened | cured at the high temperature of 150 degreeC, hardening did not advance at 100 degreeC and 125 degreeC.

Special table 2010-521564 gazette

Claims (13)

Polymerization in the presence of a monomer A having two or more radical polymerizable double bonds in the molecule and a polymerization initiator B having a carboxyl group in the molecule of 5 to 200 mol% relative to the number of moles of the monomer A Obtained by thermally curing a thermosetting resin composition containing a reactive agent (a1) containing a highly branched polymer having a carboxyl group at the molecular end and a reactive agent (b) containing a polyfunctional isocyanate compound. Cured film. A monomer A having two or more radical polymerizable double bonds in the molecule and a monomer C having a carboxyl group or a hydroxy group and at least one radical polymerizable double bond in the molecule A reactive agent (a2) containing a hyperbranched polymer having a carboxyl group at the molecular end, obtained by polymerizing in the presence of a polymerization initiator B having a carboxyl group in the molecule in an amount of 5 to 200 mol% of the number; The cured film obtained by thermosetting the thermosetting resin composition containing the reactive agent (b) containing a polyfunctional isocyanate compound. The cured film of Claim 1 or Claim 2 whose said monomer A is a compound which has any one or both of a vinyl group or a (meth) acryl group. The cured film according to claim 3, wherein the monomer A is a divinyl compound or a di (meth) acrylate compound. The cured film according to claim 2, wherein the monomer C is used at a ratio of 5 to 300 mol% with respect to the number of moles of the monomer A. The cured film according to claim 5, wherein the monomer C is a compound having at least one of either a vinyl group or a (meth) acryl group. The cured film according to claim 6, wherein the monomer C is a compound represented by the following formula [1].

(In Formula [1],
R ¹ represents a hydrogen atom or a methyl group, and R ² is a hydrogen atom, an alkyl group, or an alkyl group having 1 to 20 carbon atoms which is substituted with a hydroxy group of carbon atoms 1 to 20 substituted with a carboxyl group Represents. ) The cured film according to any one of claims 1 to 7, wherein the polymerization initiator B is an azo polymerization initiator. The cured film according to claim 8, wherein the polymerization initiator B is 4,4′-azobis (4-cyanovaleric acid). The molar equivalent of the carboxyl group of the hyperbranched polymer contained in the reactant (a1 ) is 0.01 to 10 with respect to the number of moles of the isocyanate group of the polyfunctional isocyanate compound contained in the reactant (b). The cured film according to claim 1 . The molar equivalent of the carboxyl group of the hyperbranched polymer contained in the reactant (a2) is 0.01 to 10 relative to the number of isocyanate groups of the polyfunctional isocyanate compound contained in the reactant (b). The cured film according to claim 2. Polymerization in the presence of a monomer A having two or more radical polymerizable double bonds in the molecule and a polymerization initiator B having a carboxyl group in the molecule of 5 to 200 mol% relative to the number of moles of the monomer A A method for producing a cured resin, comprising: curing a hyperbranched polymer having a carboxyl group at a molecular end obtained by the reaction with a polyfunctional isocyanate compound at an elevated temperature. A monomer A having two or more radical polymerizable double bonds in the molecule and a monomer C having a carboxyl group or a hydroxy group and at least one radical polymerizable double bond in the molecule The hyperbranched polymer having a carboxyl group at the molecular end obtained by polymerizing in the presence of a polymerization initiator B having a carboxyl group in the molecule of 5 to 200 mol% with respect to the number is increased at an elevated temperature. A method for producing a cured resin comprising reacting with a functional isocyanate compound and curing.

Images